Thesis Deciphering the Late Jurassic Paleoenvironment Through Re-Os Isotope Geochemistry of the Agardhfjellet Formation, Svalbar

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THESIS

DECIPHERING THE LATE JURASSIC PALEOENVIRONMENT THROUGH RE-OS

ISOTOPE GEOCHEMISTRY OF THE AGARDHFJELLET FORMATION, SVALBARD

Submitted by

Marisa Leigh Connors

Department of Geosciences

In partial fulfillment of the requirements

For the Degree of Masters of Science

Colorado State University

Fort Collins, Colorado

Summer 2017

Master’s Committee:

Advisor: Judith Hannah Co-Advisor: Holly Stein

Thomas Borch Øyvind Hammer

ABSTRACT

DECIPHERING THE LATE JURASSIC PALEOENVIRONMENT THROUGH RE-OS

ISOTOPE GEOCHEMISTRY OF THE AGARDHFJELLET FORMATION, SVALBARD

Accurate interpretations of environmental change throughout Earth’s history rely on robust correlations of sedimentary systems. The Late Jurassic has been difficult to correlate regionally and globally due to sparse radiometric ages and lack of cosmopolitan fossils. The rhenium-osmium (Re-Os) geochronometer provides an excellent platform to approach this problem. Re-Os geochemistry provides a way to directly date organic-rich shales which can then be used to: 1) place numerical ages on boreal fossil zones and Geologic Time Scale stage boundaries, 2) correlate with regional or global units, and 3) enhance the understanding of oceanic anoxic events (OAEs) and climactic shifts when paired with additional chemical and lithological data.

The Agardhfjellet Formation of Svalbard, Norway has multiple intervals of organic-rich mudrocks which are ideal for Re-Os geochemistry. Presented here are Re-Os ages which confirm placement of the Agardhfjellet Formation within the Late Jurassic to Early Cretaceous (157.9 ±

2.9 Ma to 141 ± 20 Ma). We provide an age immediately above the Kimmeridgian-Oxfordian boundary, within the Amoebocera subkitchini zone, at 153.2 ± 5.0 Ma in agreement with previous work. Furthermore we present evidence that: (1) the Agardhfjellet Formation was deposited in fluctuating anoxia conditions; (2) increasing initial 187Os/188Os (0.401±0.007 to

13 0.577±0.054) coupled with a decrease in δ Corg (-25.26‰ to -29.63‰) through the Late Jurassic

signifies a changing climate represented by an increase continental weathering with a warming climate and/or an increase in continental freeboard.

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ACKNOWLEDGEMENTS

First, I would like to thank my two advisors, Dr. Judith Hannah and Dr. Holly Stein of the Geosciences department at Colorado State University. Their support, patience, and guidance over the past three years have been greatly appreciated. I would like to thank my external committee members Dr. Thomas Borch and Dr. Øyvind Hammer for their understanding in the condensed time-line for defense. I would also like to thank Dr. Holly Stein and Dr. Øyvind

Hammer for braving polar bears and the Arctic in January to select the cores for my thesis, in addition to providing the CT scan work through University of Oslo. I would like to thank our research group in the AIRIE (Applied Isotope Research for Industry and Environment) Program for support and help, especially Rich Markey who provided much of the training and background needed to preform Re-Os analyses and complete my thesis.

I would also like to thank Eni Norge, Lundin Petroleum, and Aker BP (formerly Det

Norske) for their generous support through the CHRONOS project, and the AAPG Foundation

Grants-In-Aid program for their funding support through the Ike Crumbly Minorities in Energy

Named Grant – 2015.

I would like to thank my family for always encouraging me to reach for the stars (or

Earth!), especially my sister Liana for sharing in the scientific graduate school experience.

Lastly I would like to thank my husband, Gregory Connors for his unending support throughout this process. I could not have done it without you.

TABLE OF CONTENTS

ABSTRACT ...... ii ACKNOWLEDGEMENTS ...... iv LIST OF TABLES ...... vi LIST OF FIGURES ...... vii 1. INTRODUCTION ...... 1 2. GEOLOGIC SETTING ...... 4 3. METHODS AND MATERIALS ...... 9 Lithological Analyses ...... 9 Re-Os Analyses ...... 11 External Chemical Analyses ...... 12 4. RESULTS ...... 14 Core and CT Scan Description ...... 14 Thin-Section Petrography ...... 17 Re-Os Ages and Osi Results ...... 20 Rock-Eval Results ...... 24 Stable Isotope Results ...... 27 Major and Trace Element Results ...... 28 5. DISCUSSION ...... 32 Ages ...... 32 Local stratigraphy ...... 32 Bioturbation and Re-Os ages ...... 33 Regional comparisons ...... 33 Implications for the Late Jurassic timescale ...... 35 Anoxia and Restriction ...... 35 Mid-Late Jurassic Climate Shift ...... 36 6. CONCLUSIONS...... 39 LIST OF REFERENCES ...... 40 APPENDIX A ...... 46 APPENDIX B ...... 52 APPENDIX C: RE-OS ISOCHRONS ...... 53

LIST OF TABLES

TABLE 1 –CORE SAMPLE INFORMATION WITH BIOSTRATIGRAPHIC CONSTRAINTS ...... 10 TABLE 2 –UNREFINED AND REFINED RE-OS AGES WITH BIOSTRATICRAPHIC AGES ...... 21 TABLE 3 –GEOCHEMICAL DATA ...... 46 TABLE 4 –RE-OS TOTAL ANALYTICAL BLANK DATA ...... 52

LIST OF FIGURES

FIGURE 1 –REGIONAL AND SAMPLE LOCATION MAPS ...... 4 FIGURE 2 –PALEOGEOGRAPHY AND STRATIGRAPHIC RELATIONSHIPS ...... 5 FIGURE 3 –COMPOSITE SECTION OF BIOSTRATIGRAPHY AND LITHOGRAPHY ...... 7 FIGURE 4 –COMPOSITE IMAGE OF SELECTED LITHOGRAPHIC FEATURES ...... 15 FIGURE 5 –PHOTOMICROGRAPHS AND INSET SEM IMAGES ...... 18 FIGURE 6 –TWO EXAMPLES OF AGE REFINEMENT TECHNIQUES ...... 22 FIGURE 7 –REFINED RE-OS AGES WITH OSI ...... 24 FIGURE 8 –GEOCHEMICAL PLOTS WITH DEPTH ...... 25 FIGURE 9 –ROCK-EVAL DATA PLOTS ...... 26 FIGURE 10 –REDOX PROXY PLOTS...... 29 FIGURE 11 –COMPOSITE OSI FROM MIDDLE JURASSIC TO EARLY CRETACEOUS ...37

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1. INTRODUCTION

Accurate interpretations of Earth’s paleoenvironmental and biological changes throughout time rely heavily on robust correlations of sedimentary systems. In some segments of

Earth time, i.e. Late Jurassic, correlation issues arise from lack of tie-points such as cosmopolitan fossils and/or sparse radiometric ages. The rhenium-osmium (Re-Os) geochronometer provides a means of directly dating organic rich mudrocks (ORM) which, in turn, validates correlations in these previously problematic systems.

Re-Os geochemistry is increasingly useful in the study of ORM (Ravizzia and Turekian,

1989; Creaser et al., 2002; Selby and Creaser, 2003a; Cohen, 2004; Kendall et al., 2009). Several applications of the Re-Os system, in coordination with other trace metal and isotopic data, include: (1) adding precise numerical ages to system and stage boundaries (Selby and Creaser,

2003b; Selby, 2007; Xu et al., 2009), (2) providing insight into the status of anoxia within a basin (Turgeon and Creaser, 2008; Georgiev et al., 2012; Georgiev et al., 2017), (3) providing

187 188 evidence of changing climactic conditions through use of the calculated initial Os/ Osi (Osi) parameter (Ravizzia et al., 2001; Finlay et al., 2010; Georgiev et al., 2011; Xu et al., 2013), and

(4) making intra- and inter-basinal correlations (Rooney et al, 2010; Markey et al., 2017).

The Re-Os system has been proven intact through a variety of potentially disruptive processes such as hydrocarbon maturation and migration (Creaser et al., 2002) and high- temperature, contact metamorphism (Kendall et al., 2010; Kendall et al., 2011). The ideal sedimentary candidates for Re-Os geochemistry tend to be extremely fine-grained, which generally limits fluid migration, a major cause of disruption to the Re-Os system. Isochroneity in the Re-Os system is an effective indicator of preservation of primary chemical characteristics of

ORM which is critical in robust interpretation (Georgiev. et al., 2012). However, there are still

processes which can reset or overprint the Re-Os systematics in ORM (Yang et al., 2009;

Kendall et al., 2009; Rooney et al., 2011; Mahdaoui et al., 2015). These can produce non- isochronous results. In this study, a combination of chemical and lithological evidence is used to identify potential outliers and/or disturbed data points, thereby refining previously non- isochronous results and gaining useful information through Re-Os geochronology

The Agardhfjellet Formation of Svalbard, Norway offers appropriate materials for using rhenium-osmium (Re-Os) geochemistry to enhance understanding of Late Jurassic paleogeography and paleoenvironment. First, Re-Os geochemistry of regional correlatives to the

Agardhfjellet Formation, including the prolific source rocks of the Hekkingen Formation

(southern Barents and Norwegian Seas), the Kimmeridge Clay (North Sea and the United

Kingdom), and the Staffin Formation (Isle of Skye, UK) have been characterized by previous studies (Cohen et al., 1999; Selby, 2007; Markey et al., 2017; Georgiev et al., 2017). These provide regional, chronostratigraphic benchmarks for correlation and an opportunity to constrain the ages of Late Jurassic stage boundaries that are currently based on bio- and magentostratigraphy (Gradstein et al., 2012).

Second, sparse radiometric ages of the Late Jurassic coupled with limited connectivity between Tethyan, Proto-Pacific and Boreal marine realms have prevented global correlation of fossils, specifically ammonites, which provide the best-defined fossil zones for the Late Jurassic

(Cope, 2008; Gradstein et al., 2012). While individual ammonite zones have been well characterized, they have limited overlap not only inter-realm but intra-realm (Page, 2008). The biostratigraphy of the Agardhfjellet Formation has been well defined by previous workers

(Wierzbowski et al., 2011; Koevoets et al., 2016). Using this biostratigraphy in conjunction with

Re-Os geochronology can tie Boreal ammonites into the global time-scale.

Third, combining Re-Os geochemistry of the Agardhfjellet Formation with additional chemical and lithological data will enhance paleoenvironmental interpretations of the Boreal realm, including the duration of local anoxia and changes in paleoclimate. The record of Middle to Late Jurassic climate change has been documented in correlative units by multiple workers

(e.g. Ditchfield, 1997; Abbink et al., 2001; Gröcke et al., 2003; Georgiev et al., 2017). This growing body of evidence shows a period of warming, increased chemical weathering, and overall sea-level rise on a global scale. In order to understand how the Boreal realm in Svalbard fits with these trends it is imperative to have robust correlations; these can be provided by Re-Os geochemistry.

2. GEOLOGIC SETTING

The Agardhfjellet Formation is defined on the high-arctic archipelago of Svalbard,

Norway (Fig. 1A), marking the base of the Middle Jurassic to Early Cretaceous Adventdalen

Group in central and southwestern Spitsbergen (Dypvik et al., 1991; Mørk et al., 1999).

Figure 1-Reginoal and Sample Location Maps. A) Location map showing Svalbard (black outline) and study area (red outline). B) Locations of Longyearbyen CO2 Lab drill hole 2 (Dh2) and drill hole 5 (Dh5) with generalized surficial geology after Braathen et al., 2012. The ORM of the Agardhfjellet Formation were deposited throughout the Middle to Late Jurassic in a shallow to deep, marine shelf setting off the coast of present-day Greenland (Dypvik et al.,

1985, 2002) (Fig. 2A). The Boreal region as a whole experienced intermittent anoxia throughout the Middle to Late Jurassic (Dypvik, 1985; Nagy et al., 1988) leading to the deposition of thick packages of organic-rich sediments within the Agardhfjellet Formation and its correlatives including the Måsnykan, Fuglen, and Hekkingen Formations of Barents and Norwegian Seas

(Fig. 2B).

Figure 2-Paleogeography and Stratigraphic Relationships. A ) Paleogeographic reconstruction (after Torsvik et al., 2002) with Re-Os study locations. Star – this study. Circles – previous AIRIE studies in the Hekkingen Formation (Markey et al., 2016; Georgiev et al., 2016) Square – Staffin Bay Formation (Selby, 2007). Arrow points off-image to Kimmeridge Clay at Dorset (Cohen et al., 1999). B) Regional stratigraphic correlations based on Dypvik et al. 2002 and Smelror et al., 2001. Spitsbergen and adjacent areas experienced a variety of igneous and tectonic activity after the deposition of the Agardhfjellet Formation. Cretaceous dolerite sills related to the High Arctic

Large Igneous Province are present in Dh5; most, however, intrude the Triassic and Middle

Jurassic units more than 200 m below the Agardhfjellet Formation. This activity led to regionally elevated geothermal gradients estimated up to 50˚ C/km (Senger et al., 2014a; Senger et al.,

2014b; Marshall et al., 2015). The present-day geothermal gradient has been measured at 40˚

C/km (Braathan et al., 2012). The Agardhfjellet Formation and overlying Rurikjfellet Formations were deposited in a tectonically quiet basin. Throughout the Paleogene, however, transpressional deformation related to the opening of the Greenland Sea generated large thrust belts and created the Tertiary Central Basin on Spitsbergen (Braathen et al., 1999). In the early Oligocene the

Agardhfjellet Formation reached its peak depth of greater than 3000 m (Michelsen and

Khorasani, 1991) followed by relatively rapid exhumation and uplift to its present depth within the Tertiary Central Basin at Longyearbyen.

Core segments for this study were collected in organic-rich mudstone and claystone intervals of the Agardhfjellet Formation from two wells of the Longyearbyen CO2 Lab project near Longyearbyen, Svalbard. The Agardhfjellet Formation outcrops to the north and east of

Longyearbyen whereas in the study area it is in the subsurface (Fig. 1B). For the CO2 Lab project two clusters of wells were drilled seven kilometers apart to test for potential CO2 storage in the

Early Jurassic Kapp Toscana Group, which underlies the Agardhfjellet Formation. Core was chosen from one well in each cluster: Dh2 near the Svalbard airport and Dh5 to the south of

Longyearbyen (Fig 1B). At Dh2 the Agardhfjellet Formation spans a depth of 732 m to 481 m.

At Dh5 the base of the Agardhfjellet is placed at 671 m depth while the top is not well-defined due to a thick interval of diamictite (Koevoets et al., 2016). Within the study area the

Agardhfjellet Formation dips to the NW so that correlative strata in Dh2 are 60 m deeper than

Dh5 (e.g. Dh2 660 m ≈ Dh5 600 m; Fig. 3). A regional detachment zone has been identified in the uppermost Agardhfjellet Formation within both drill holes (Braathen et al., 2012), but this starts several 10’s of meters above the shallowest sample collected for this study.

The Agardhfjellet Formation at Longyearbyen is divided into four members including, from base to top, the Oppdalen, Lardyfjellet, Oppdalssåta, and the Slottsmøya (Dypvik et al.,

1991; Koevoets et al, 2016). All members are recognized in the drill core (Fig. 3). The Oppdalen

Member, which unconformably overlies the coarse-grained Kapp Toscana Group, consists of silty to sandy mudstones with intermittent siderite horizons. Kepplerities svalbardensis was identified within the lower Oppdalen Member (Fig. 3) making it uppermost Bathonian in age.

The Lardyfjellet Member is chiefly organic-rich black shale with intermittent siderite horizons. It coarsens upward at the top into greyish, siltier layers. Within the Lardyfjellet Member there are abundant fossils including the fish bones, bivalves, microfossils, and the Lower Kimmeridgian ammonite Amoeboceras subkitchini (Fig.3).

Figure 3-Composite section of Biostratigraphy and Lithostratigraphy. Lithostratigraphy and biostratigraphy of the Agardhfjellet Formation from Dh5 and Dh2 (after Hammer, written communication, 2014; Koevoets et al., 2016). Core intervals used for analyses in this study marked on right. Length of collected core sample in parentheses below intervals.

The Oppdalssåta Member is the most varied lithologically. It consists of several coarsening up sequences which grade from shale with variable organic material into sandy siltstones with intermittent glauconitic horizons. The Upper Kimmeridgian ammonite,

Amoeboceras elgans, was identified in the Oppdalssåta Member (Fig.3). The Slottsmøya

Member has the fewest organic-rich intervals and is chiefly grey shale with intermittent siderite horizons. The Middle Volgian ammonites of Pavlovia sp. and Dorsoplanities sp. are found in the

Slottsmøya as well as plentiful bivalves, fish bones, and woody debris (Hammer, 2014; Koevoets et al., 2016; Fig. 3).The Volgian stage is defined from Boreal fossils and correlative to the

Tithonian and lowermost Berriasian stage. The Slottsmøya member is unconformably overlain by the widespread Myklegardfjellet bed of the Early Cretaceous Rurikfjellet Formation.

3. METHODS AND MATERIALS

Lithological analyses

Seven segments of whole drill core ranging from 8 to 30 cm in length were chosen from organic-rich shale intervals of the Agardhfjellet Formation in Dh2 (N=2) and Dh5 (N=5) by Dr.

Holly Stein (Table 1).Segments were selected for lack of evidence of bioturbation (well- laminated samples), lack of visible structural deformation (folding, faulting, joints), and potential for high organic matter (black shale). Identified segments were prioritized for proximity to: (1) potential stage boundaries (e.g., Oxfordian-Kimmeridgian), (2) proximity to upper and lower formational boundaries or (3) an identified fossil zone (e.g., A. subkitchini). Dr. Øyvind Hammer at the University of Oslo provided both biostratigraphy and x-ray computed tomographic scans

(CT) for core segments. Core was then taken to Colorado State University for sampling and Re-

Os analyses.

Whole core segments were photographed and described before and after splitting with a diamond-tipped saw. One half of each core segment was saved for reference while the other half was used for sampling. Four polished thin-sections (one each from Dh2-660, Dh2-674, Dh5-600 and Dh5-613) were made for detailed petrographic study of correlative segments of Dh5 and

Dh2. Optical microscopy was performed at Colorado State University. Framboid size ranges were determined by reflected light microscopy and measurements made with digital imager calibrated using ProgRes CapturePro 2.8.8 software. SEM and electron microprobe analyses were performed at the University of Oslo. SEM and microprobe were used to identify compositions of select grains. Multiple samples < 1 cm thick were selected from each core

segment for Re-Os analyses as well as additional geochemical analyses. Individual samples of 5 to 10 grams were either taken along parting laminations or, in the case of well indurated samples

(Dh2), cut using a diamond tipped saw. These samples were rinsed with DI water and dried before pulverizing using a corundum mortar and pestle and an agate ball mill to produce a fine, homogenized powder. The powder was split for Re-Os, trace element, total organic carbon

(TOC), Rock-Eval pyrolysis, and stable isotopes analyses.

Re-Os Analyses

Rhenium-osmium geochemistry was performed at the AIRIE (Applied Isotope Research for Industry and Environment) Program at Colorado State University in accordance with previously defined procedures described briefly below (Georgiev et al., 2015). A total of 41 powdered samples, ranging from 300-500 mg, were used to obtain the seven isochrons reported here. A calculated amount of Re and Os spike solutions, enriched in 185Re and 190Os respectively, were added to samples prior to digestion for subsequent calculation of sample Re and Os concentrations by isotope dilution. Samples were digested in 11 mL of CrO3-H2SO4 for 48 hours in sealed Carius tubes at 240˚C. Chemical separation and purification of Re and Os were accomplished using H Br extraction and microdistillation (Os), followed by anion exchange column separation (Re). Re and Os were loaded onto outgassed, high-purity, platinum filaments for analysis with a barium activator solutions, Ba(NO3)2 for Re and Ba(OH)2 for Os. Isotopic ratios were measured by negative thermal ionization mass spectrometry (NTIMS) using Triton mass spectrometers at the AIRIE Program, CSU. Each batch of sample measurements also included a total analytical blank (TAB) and in-house standards.

Measured isotopic ratios are corrected for oxygen isotope contributions, mass fractionation (Os), TAB contributions, and spike contributions. Re contributions from blanks

ranged from 0.05% to 4.9% with a mean of 0.8%. Os contributions from blanks ranged from

0.062% to 0.31% with a mean of 0.15%. Blank contributions to individual samples can be seen in appendix A with blank information in appendix B. Re and Os standards for these samples are:

185Re/187Re = 0.59717 ± 0.00056, 1σ, n = 9; 187Os/188Os = 0.12375 ± 0.00016, 1σ, n = 9). These are statistically consistent with AIRIE long-term averages.

Uncertainties calculated for Re-Os analyses include weighing errors, errors on spike calibrations, errors on measured ratios, an error magnifier based on spiking ratios, and uncertainty in blank corrections. Isochrons were calculated using Isoplot 3.75 (Ludwig, 2012).

Resulting uncertainties in ages are based on the fit of the regressed line. Uncertainty in the

187Re decay constant (1.666 x 10-11 yr-1 ± 0.31%) was added to reported ages.

External Chemical Analyses

Leco TOC and Rock-Eval pyrolysis results were obtained from Geomark Research Inc.

TOC, S1, S2, S3, and TMax were reported for 41 samples along with a calculated vitrinite reflectance (from TMax) and calculated percent carbonate from loss of mass after initial treatment with HCl. The S1 peak represents the free hydrocarbons in rock. The S2 peak represents the volume of hydrocarbons produced during the pyrolysis process which is used to calculate the hydrogen index (HI) and is an estimate of hydrocarbon generation potential. The S3 peak represents produced CO2 from pyrolysis and is used to calculate the oxygen index (OI).

TMax is determined from the temperature at the apex of the S2 peak.

Stable isotope analyses for selected samples were obtained from Iso-Analytical Limited,

Crewe, United Kingdom. Analyses were performed using an Elemental Analyser-Isotope Ratio

Mass Spectrometer (EA-IRMS) for bulk δ15N (n=14), δ34S (n=15), and organic δ13C (n=15); and a Continuous Flow- Isotope Ratio Mass Spectrometer (CF-IRMS) for carbonate δ18O and δ13C

18 13 13 (n=12). Measurements were reported relative to V-PDB for δ Ocarb, δ Ccarb, δ Corg V-CDT for

δ34S, and air for δ15N.

Selected major and trace element analyses were obtained commercially through

Activation Laboratories, Ontario, Canada. The Ultratrace 6 method was used to obtain 61 trace and major element concentrations from 41 shale samples. Samples were processed using multi- acid total digestion and measured using ICP-AES for major elements and scandium and ICP-MS for remaining trace elements. Details of the 61 elements can be found in appendix A.

4. RESULTS

Core and CT Scan Descriptions

Descriptions for the Dh5 core begin with the uppermost sample from the Slottsmøya

Member (Dh5-489) and ends with the lowest sample (Dh5-658) from the Oppdalen Member.

Where present, all laminations are perpendicular to the length of the core.

Dh5-489, in the upper-middle Slottsmøya Member, is a dark-grey, moderately-indurated, silty, claystone with trace visible (< 1 mm) pyrite, mostly associated with partial carbonate replacement. Although bedding is not observable in hand sample, CT scans show minor laminations visible with some scattered framboids and agglutinated forams.

Dh5-542, in the upper Oppdalssåta Member, is a dark grey to black, moderately- indurated mudstone. Small pyrite nodules/framboids (< 1 mm), Teichnitas burrows, and agglutinated foraminifera are visible both in CT scan and in hand sample (Fig. 4A). These are most prevalent between 542.28 m and 542.40 m. Small onychites (> 1 cm) are also present in some laminae. A slickenside is visible at the top of the core segment (542.28 m, Fig. 4B).

Dh5-600, in the upper Lardyfjellet Member, is a black to dark grey, moderately- indurated, clay-rich mudstone. Discontinuous laminations are difficult to discern in hand sample.

In CT scans, laminations are highly visible and generally defined by agglutinated foraminifera and pyrite nodules.

Dh5-613, in the middle Lardyfjellet Member, is a black to dark grey, well-indurated, mudstone. Several wavy, continuous to discontinuous, silty, laminae are present in the upper ~10 cm and decrease in frequency as well as thickness (< 1 mm) with increasing depth. Macrofossils are present and include a bivalve (10-12 mm) replaced by pyrite at 613.62 m, and

Figure 4-Composite image of selected lithographic features. A) Agglutinate foraminifera from Dh5-542 comparing photographed core (left) to CT scan (right). B) Slickenside located at 542.28 m in Dh5. C) Pyritized fossils (black circles) at 613.32 m and A. subkitchini mold at 613.68 m (right) from Dh5. D) Hydrocarbon (HC) leached into paper towel from silty facies and fractures from Dh5-613. E) Pyritized and dolomitized burrows from Dh5-658 in 3D-CT scan (left) and slabbed core (right). F) Laminations of Dh2-674 in slabbed core and CT scans. CT scans are set for different contrasts. In both images laminations are easily visible sub-parallel to cross-section of core. A Fe-dolomite bivalve is visible in the lowest portion of the 3D-scan. the imprint of an ammonite (A. subkitchini) at 613.68 m (Fig. 4C). Several fractures sub-parallel to core and a semi-vertical fracture developed after sawing. A few of these fractures within siltier laminations show hydrocarbon leaching into paper towels after drying from sawing process (Fig.

4D).

Dh5-658,i n the middle Oppdalen Member, is a fissile, dark grey, silty-claystone. Pyrite is highly abundant throughout this core, chiefly replacing burrows. CT scans show that burrows are predominantly horizontal to sub-horizontal single-track as well as a few vertical, single-track burrows, and few branching-downward burrows (Fig. 4E). These have been interpreted as

Planolites and possible Chondrities although branching is rare. Several of the larger burrows have a dolomite core indicating only partial pyritization took place (Fig. 4E). The Dh5-658 core segment comes from an interval below a siderite hardground and itself has been cemented by siderite. This has prevented significant compaction which is also reflected in the preserved geometries of the burrows.

Both segments of studied core from Dh2 come from the Lardyfjellet Member of the

Agardhfjellet Formation, and are correlative to the Lardyfjellet Member core in Dh5 (Fig. 3).

Dh2-660 is a black to dark grey, well-indurated, silty-claystone. Parallel, continuous to discontinuous, silty laminations are readily visible in hand-samples and in CT scan. Laminae are at an angle of ~95˚ to the core length. Several macrofossils, most likely bivalves, are present in the lower 10 cm, parallel to bedding. These are generally dolomite with or without partial pyritization. A 2 cm gap in the core between the lower and upper segment was taken by other workers to identify a bivalve which had been buried in an upright position. Above this interval, the upper 6 cm of core lacks obvious macrofossils.

Dh2-674 is a black to dark grey, well-indurated, silty claystone. Thin, continuous, silty laminations at ~85 ˚ to the length of the core are well expressed in both hand sample and CT scan at (Fig. 4F). While the core as a whole coarsens upward, individual laminations show fining upwards. A slickenside appears at the top of the core segment, 674.08 m.

Thin-Section Petrography

Thin-sections of the Lardyfjellet Formation reveal detailed information through optical microscopy and additional electron microprobe and scanning electron microscope (SEM) analyses. The following descriptions compare findings from correlative units in Dh2 and Dh5.

The upper correlative intervals are Dh2 660.83 m- 660.865 m and Dh5 600.32 m-

600.355 m. In both cases, thin-sections were taken near the top of an identified organic-rich mudstone below the transition to the coarser upper siltstone of the Lardyfjellet Member. Distinct muddy and silty facies were identified within the Dh5-600 thin section, similar to those in Fig

4D. The muddy facies is poorly-laminated with ~1-5% medium silt to very-fine sand-sized clasts. Clasts are primarily subangular to subrounded quartz and muscovite. The silty facies is a silty claystone with 10-15% clasts. Clasts are ~5% agglutinated foraminifera and 10% clastic grains (angular to subangular quartz, muscovite, and trace detrital intraclasts of smectite and illite). In both facies, muscovite flakes are parallel to sub-parallel to bedding. Pyrite is present in two main forms: framboids and replaced microfossils. Disseminated framboids occur throughout the thin sections and clustered framboids appear near algal material and microfossils (similar to

Fig. 5A, B). Framboids from clusters average 16.8 ± 10.7 µm (n=92; 2σ), whereas disseminated framboids are generally smaller at 11.2 ± 9.5 µm (n=40; 2σ).

Facies in Dh2-660 are similar to Dh5-600 although overall Dh2-660 has a higher proportion of silt. Again, two facies are recognizable: a muddy facies and a silty facies. The muddy facies is 5-10% fine silt to very-fine sand, 1-5% organic material and the remaining fraction clay-sized material. Silt and sand-sized clasts are angular to subangular quartz and muscovite, bioclasts, and trace detrital clays including smectite. The silty facies is generally 10-

20% fine-silt to very-fine sand of similar composition to the muddy facies, with 1-2% organic

Figure 5-Photomicrographs and inset SEM images. A) Pyrite framboid cluster in Dh2-660. Elongate grains are compacted around cluster. B) Microbial mats in Dh2-613 with associated pyrite. C) Sub-mm siltstone laminations within the silty facies of Dh2-674. D) Bioclasts from Dh2-674 which have been recrystallized as Fe-dolomite. E) Bone fragment with infilling kaolinite and apatite, and a pyritized bioclast in Dh2-674. F) Cluster of pyrite and sphalerite from Dh2-674. Pyrite shows overgrowth textures (See “Thin-section petrography) for more detail). Key abbreviations: py-pyrite, mu-muscovite, qtz-quartz, af-agglutinated foraminifera, mm-microbial mat, dol-dolomite, kao-kaolinite, ap-apatite, sp-sphalerite, RL-reflected light, PPL-plain polarized light, XPL-crossed-polarized light, SEM-scanning electron microscopy photograph. material and the remaining fraction clay-sized material. This facies also shows discontinuous, thin (10-100 µm) laminations of 40-50% silt-sized particles with the remainder clay and organic material. Silt-rich laminations commonly show scoured contacts with underlying beds. Pyrite is in the form of framboids with few microfossils. In contrast to Dh5-600, disseminated framboids

are dominant. Disseminated framboids are 8.9 ± 8.5 µm (n=99; 2σ) while clustered framboids are 30.8 ± 23.2 µm (n=24; 2σ). Phosphatic bone fragments of up to 500 µm in length, most likely from fish, are present throughout section but more concentrated in the silty facies.

The second pair of correlative samples is Dh5 613.765-613.80 m and Dh5 674.095-

674.125 m. Dh5-613 shares a similar silty facies to Dh5-600, however there are differences in the muddy facies. The muddy facies is <1% medium to very-fine silt consisting of sub-angular to sub-rounded quartz and trace muscovite. Several thin layers of discontinuous microbial mats that host most of the framboids in this section are present in the muddy facies (Fig. 5B).

Disseminated framboids exist throughout both facies although no significant size difference occurs between these and the mat-hosted framboids. Combined, framboids have a mean diameter of 9.1 ± 5.2 µm (n=149; 2σ). Carbonate bioclasts and long fragments of bone (probably fish) are present in both facies and lie parallel to sub-parallel to laminations.

Dh2-674 has two facies (muddy and silty) but overall is much siltier than Dh5-613. The muddy facies is 15-30% silt to very-fine sand. Sub-angular to sub-rounded quartz makes up a majority of the clasts with trace muscovite and detrital clays. Microbial mats define several continuous to discontinuous laminations within the muddy facies. The silty facies occurs in discrete, continuous to discontinuous laminations, usually scoured into the muddy facies (Fig.

5C). These laminations are 50-80% fine silt to fine sand with an average of coarse silt. Clasts are chiefly angular to sub-rounded quartz with muscovite and detrital clay-intraclasts. Bioclasts are common in both facies. Several macrofossils (2-3 mm) are recrystallized as ferroan dolomite while microfossils tend to be replaced by pyrite (Fig. 5D and, E). Bone fragments typically have pore spaces filled with kaolinite or crystalline apatite (Fig. 5E). Framboids occur as disseminated grains (12.4 ± 8.0 µm; n=74; 2σ) and in clusters around microbial mats (17.0 ± 9.6 µm; n=36;

2σ). One cluster of sulfides at ~674.087 m displays a different texture than previously encountered (Fig. 5F). Sphalerite and pyrite are both present. The internal structure of the pyrite is pitted whereas the rim is unblemished. From SEM analyses, pyrite within this cluster shows measureable amounts of Ni and Cu whereas framboids nearby do not. Associated sphalerite houses measureable Cd.

Re-Os Ages and Osi Results

Seven Re-Os isochrons are reported for the Agardhfjellet Formation (Table 2). These isochrons have been refined to omit identifiable outliers using a combination of three methods.

The first method involves identification of samples located next to geologically induced fractures which provide potential conduits for fluids in the subsurface. In the core extraction and slabbing processes, fractures can be induced which are not geological in nature. These induced fractures do not contribute to Re-Os disrupting fluid movement, and therefore can be used confidently in the sampling process. CT scans were used to locate bedding plane fractures, produced by relieving over-burden upon core extraction, and to identify slabbing-induced fracturing as the core was scanned intact. For example, sample 489.33 m from Dh5 was found to be located on a geologic fracture (Fig. 6A). Removal of this point decreased the uncertainty on the Re-Os age by

10 Ma (Fig. 6B and, C). The second method is to identify sub-mm changes in lithology. The grainsize of ORMs generally provide baffles to fluid movement. Because of this, even the thinnest siltstone intervals can provide potential conduits for fluid movement (ex. Fig. 4D) that can affect or over-print the depositional Re-Os signature within sub-mm laminae. The third method of refinement is to identify chemical outliers, generally within the redox sensitive elements. Outliers which have significantly different chemical signatures than the surrounding

Figure 6-Two Examples of Age Refinement Techniques (See “Re-Os Ages and Osi Results” for discussion) A) CT scan (left) and photograph of slabbed core (right) showing identified types of fractures. Dh5-489 has naturally occurring geologic fractures (GF) and induced fractures: bedding-plane fracture (BPF) and slabbing fracture (SB). The 489.33 m sample was located along a GF. Removal of this point resulted in an uncertainty reduction of 10Ma B) Unrefined isochron from Dh5-489. C) Refined isochron. D) Trace element plots show abrupt changes in chemistry to identify chemical outliers (Triangles = Dh5. Squares = Dh2). Outliers were identified in Dh2 at 660.96 m (red circles) and Dh5 at 613.70 m (blue circles). Removal of the 660.96 m sample from the Dh2-660 isochron results in an uncertainty reduction of 11.7 Ma. E) Unrefined isochron of Dh2-660. F) Partially refined isochron from Dh2-660 with only 660.96 m removed.

samples can be caused by a variety of processes including localized fluid interaction, and/or detrital influences. Two chemical outliers are identified at Dh2-660.96 m and Dh5-613.70 m

(Fig. 6D). The removal of a single chemical outlier in Dh2 at 660.96 m resulted in the reduction of uncertainty in age by 10.7 Ma (Fig. 6E and F). Unrefined and refined ages for all seven core segments including which samples were removed for refinement are in Table 2.

Re-Os ages from the Agardhfjellet Formation are a mix of Model 1 and Model 3 fits.

Model 1 ages suggest that all of the uncertainty lies in the analytical uncertainties while Model 3 ages suggest geologic influences contribute to the uncertainty. Of the seven refined isochrons in the Agardhfjellet Formation, five have been identified as depositional ages (Dh2-660,674 and

Dh5-489, 542, 658) and two have a high likelihood of over-printing or resetting because of diagenetic influences (Dh5-600 and Dh5-613). The five depositional isochrons place the

Agardhfjellet Formation in the Middle Jurassic to earliest Cretaceous (Fig. 7, Table 2). Re-Os ages place the upper Oppdalen Member in the Oxfordian, the middle to upper Lardyfjellet

Member in the Kimmeridgian, the lower Oppdalssåta Member and the middle Slottsmøya

Member in the Volgian. The derived Osi from these isochrons show a steady increase in this ratio through the Middle to Late Jurassic and potential decrease in the early Cretaceous indicating shifting inputs or Re and Os in the ocean over this time. Although Dh5-600 and Dh5-

613 have Early Cretaceous Re-Os ages, the biostratigraphy and the correlative section in Dh2

(674) both agree with a Kimmeridgian age (Table 2).The Model 1 ages from these Dh5

Lardyfjellet Member samples suggest that the they show overprinting of the depositional ages events in the Early Cretaceous.

Including all samples, rhenium varied from 55.7 ppb to 3.6 ppb and osmium varied from

0.732 ppb to 0.206 ppb (Fig. 6D). There is somewhat limited spread in the 187Re/188Os ratios

Figure 7-Refined Re-Os ages with Osi. Re-Os ages shown in comparison with biostratigraphic ages from GTS 2012 and GTS 2004 (italics). Osi derived from isochron regressions reported to right. (616 to 119) and 187Os/188Os ratios (2.2 to 0.637) across the Agardhfjellet Formation, negatively impacting the precision of the isochron.

Rock Eval Results

The ORM of the Agardhfjellet Formation range in TOC from 1.19% to 11.7% (Fig. 8). A general decrease can be seen from the lower Lardyfjellet samples up into the Slottsmøya

Figure 8-Geochemical Plots with Depth. Geochemical plots from the Agardhfjellet Formation. Percent carbonate is a calculated value from the Rock-Eval preparation process (see “External Chemical Analyses” for details). Triangles = Dh5. Squares = Dh2. Samples are listed in stratigraphic order. Core depths listed as Dh5 (Dh2). Trends are discussed in Results section of text. samples. Intervals with the highest TOC are the Lardyfjellet Member samples ranging from

6.36% to 11.7% in Dh5 (600 and 613) and 6.11% to 11.7% in Dh2 (660 and 674). Low TOC intervals occur in the Slottsmøya and Oppdalen Members ranging from 1.77%-2.5% (Dh5-489) and 1.19% to 1.37% (Dh5-658) respectively. TOC in the Oppdalssåta Member ranged from 4.71 to 7.95% (Dh5-542). The hydrogen index (HI = mg HC/g TOC) and oxygen index (OI = mg

CO2/g TOC) range from 31.3 to 126.5. and 2.4 to 23.1 respectively (Appendix A). Samples generally fall in the Type III kerogen field on the Kerogen Quality Plot indicating strong land- plant derived input to the organic matter (Fig. 9A). Samples from Dh5-658 fall just into Type IV kerogen (inertinite), although this may be a factor of high maturity as indicated by the Pseudo

Van Krevelen Plot (Fig. 9B). Maturity proxies, including the production index (PI =

Figure 9-Rock-Eval Data Plots A) Agardhfjellet Formation plots within Type III kerogen indicating strong land-material influence. B) Agardhfjellet samples show high maturity. C) Production index shows high maturity in Dh5-489,542 and 658. Lardyfjellet Member samples (Dh2-660,674 and Dh5-600,613) show decreasing maturity with depth. See “Rock-Eval Results” for discussion. D) The Kerogen Conversion Plot shows all samples in the wet condensate field.

Definitions of S1-S3 and Tmax in “External Chemical Analysis” section. .

S1/(S2+S1)), and Kerogen Conversion (PI vs TMax), indicate the Agardhfjellet Formation ranges from the late oil/condensate to gas prone window (Fig. 9C and, D). Maturity indicated by the production index does not directly follow a depth relationship. In fact, the relationship is generally inverse to depth through the Lardyfjellet Member section (Fig 9D). One explanation for this relationship could be the relatively short-term deep burial of the Agardhfjellet Formation.

Burial below 1.5 km did not begin until ~65 Ma with the opening of the Greenland Sea.

Although the Agardhfjellet Formation reached a depth of > 3 km, it was rapidly uplifted to ~1.5 km by 20 Ma and continued to uplift through the present-day (Micklesen and Khorsani, 1991).

Because of this relatively rapid burial and exhumation, samples with higher TOC, such as the

Lardyfjellet Formation, may not have matured as fully as samples with low TOC, such as the

Oppdalen and Slottsmøya Members.

Stable Isotope Results

13 13 18 34 Stable isotopes of δ Corg, δ Ccarb, δ Ocarb, and δ SV-CDT show several trends. Organic

13 stable carbon (δ Corg) shows a decrease (Fig. 8) from the older Oppdalen Member (-25.25‰) to the younger Slottsmøya Member (-29.63‰). Inorganic carbon and oxygen are both highly negative and variable throughout the Agardhfjellet Formation (Fig. 8) indicating post-

13 depositional influences. The δ Ccarb was lowest in Dh2-674 (-13.58‰ and -11.80‰) and the

13 highest in Dh5-542 (-7.17‰). Similarly, the lowest values of δ Ocarb were also in Dh2-674 (-

34 13.92‰ and -14.54‰) and highest in Dh5-542 (-7.99‰). The δ SV-CDT values are highly

34 variable and ranged from -7.37‰ (Dh5-613) to -33.49‰ (Dh5-658). Generally lower δ SV-CDT

34 values correlate with high pyrite content (Dh5-658) and higher δ SV-CDT correlate with higher wt.% TOC (Fig.8).

Major and Trace Element Results

Major and trace element analyses show variability among the members of the

Agardhfjellet Formation. Iron generally mirrors the sulfur content of samples. The highest concentrations of iron appear in samples with abundant visible pyrite and siderite (Dh5-658).

Detrital proxies such as Al (wt.%) and Ti/Al (ppm/%) document variability in the general detrital input to Dh5-542, 600 and 613 as well as Dh2-674 (Fig. 8). Dh5-489 shows decreasing Al, increasing Ti relative to Al, and constant Zr/Al (ppm/%). This could be explained by a grain-size increase up-section. Dh5-658 shows consistency in all three proxies. The apparent outlier in

Dh5-658 for Al-based proxies is a product of the way data over the detection limit were plotted

(See Appendix A-Trace and Major Element for details).

Figure 10 shows selected redox-related proxies. The Agardhfjellet Formation is enriched in many chalcophilic and siderophilic element compared to average shale (Wedepohl, 1971)

(Fig. 10A). Enrichment factors (EF) were calculated by normalizing Agardhfjellet samples to Al as a proxy for detrital influx and then dividing by Al-normalized average shale (i.e.

(ElementAF/AlAF)/(ElementPAAS/AlPAAS)). In general, redox sensitive elements such as U, V, and

Mo show enrichment in the Lardyfjellet and Oppdalssåta Members, especially in Dh2-674, and depletion or average values in the Slottsmøya and Oppdalen Members. Most EF’s range over an order of magnitude for the Agardhfjellet Formation; Co, however, is consistent and depleted

(0.310 to EF <0.05. While redox sensitive elements are generally enriched compared to average shales, many are depleted when compared to average Late Jurassic to Early Cretaceous correlative Norwegian shales (Black line-

Fig. 10A) (Lipinski et al., 2003;Markey et al., 2017-Fig 5). The exception is silver which is

Figure 10-Paleoredox Proxy Plots. (see “Trace and major elements” for details). A) Enrichment factor (EF) for various trace elements of Agardhfjellet Formation in relation to average shale (Wedepohl, 1971). The thick black line is an average for Norwegian, Late-Jurassic to Early Cretaceous black shales (Lipinski et al., 2003). B) Redox proxy ratios with depth. Light grey zones indicate values associated with dysoxic conditions. Dark grey is associated with anoxic to euxinic conditions. Triangles=Dh5, Squares=Dh2. C) Fe versus S concentration plot. S/Fe = 1.15 is the pyrite line. D) Fe-S-TOC normalized concentration plot. The appearance of Dh5-489 and Dh5-658 in the oxic field of this plot and the previous plot is deceptive because Fe is included in non-sufide phases. E) Framboid diameter data in the Lardyfjellet Member as box-and-whisker plots. Arithmetic means listed with sample size. All sections indicate anoxic to dysoxic conditions within the sediment column.

highly enriched compared to average shale, and enriched compared to Norwegian shale within the Lardyfjellet Member.

Chemical redox proxies for the Agardhfjellet Formation show variable results. The Fe versus S concentration plot and the Ni/Co proxy show two sections from the Agardhfjellet

Formation have samples which fall into the oxic field (Dh5-489, 658) while the rest of the samples fit in the dysoxic to anoxic fields (Fig. 10B,C). Lines regressed through the samples of

Dh5-489 and 658 on the Fe vs S plot show similar slopes to that of the pyrite line (S/Fe = 1.15) with intercepts ~2.3 wt.% Fe. This indicates that the degree of pyritization was high, but S was limiting; therefore, Fe was included in other phases such as high-Fe dolomite and/or siderite, both of which are abundant in the Agardhfjellet Formation. When normalized to TOC, Dh5-489 and 658 still fall into the oxic section (Fig. 10D). The higher V/Mo ratio in Dh5-658 also indicates that sulfate-reduction was not a dominant process and as such sulfur could be unavailable for pyrite formation (Fig. 10B). Two common redox proxies, U/Th and V/Cr, generally show core as oxic with a few dysoxic samples from Dh2-674, Dh5 613 and 658 (Fig.

10B). These proxies could be misleading as they are sensitive to additional parameters such as mineralogy, (i.e. U substitution in apatite which is a common mineral in Dh2-674) and provenance of sediments (i.e. Cr is higher in mafic sourced sediments and clays), (Tribovillard et al., 2006). Using the V/(V+Ni) proxy, all samples fit within the anoxic category (Fig. 10). Re/Mo has been used to define the degree of anoxia where low values are anoxic to euxinic and high values are suboxic to oxic (Crucius et al., 1996; Lipinski et al., 2003). Samples from the

Agardhfjellet Formation show variable results in this metric as well. Cores from Dh5-658, 542 and Dh2-674 all show deceases in the Re/Mo ratio from suboxic to anoxic upsection, whereas the other samples are more scattered within these categories (Fig. 10B). Non-depositional ages

are associated with scatter in the Re/Mo ratios whereas depositional ages show steady trends in

Re/Mo ratios.

5. DISCUSSION

Ages

Local stratigraphy

Depositional ages indicate the Agardhfjellet Formation was deposited over at least 15 Ma from late Jurassic (157.9 ± 2.9 Ma) to early Cretaceous (141 ± 20 Ma). Ages are in general agreement with identified fossils. Two sections, the Slottsmoya (Dh5-489) and upper middle

Lardyfjellet (Dh2-660), have slightly younger nominal ages, but are still within uncertainty of the expected ages (Table 2). A condensed section of ~7 Ma in 12 m is recorded within the

Oppdalan member between the upper Bathonian Kepplerities svalbardensis and the late

Oxfordian Re-Os age recorded from Dh5-658. This could contain one long or several shorter hiatuses in deposition, not unlike much of the Barents Sea where Middle Oxfordian strata are missing (Smelror et al., 2001). Changes in sea level from upper Bathonian to upper Oxfordian may have had a stronger effect on the Agardhfjellet Formation because of its near-shore setting, in contrast to the deeper shelf environment offshore.

Local alteration in the Lardyfjellet Formation at Dh5 is needed to account for the discrepancy of depositional ages in Dh2 and non-depositional ages in Dh5 (Fig. 7). Core from

Dh5 shows more parting and structural fractures than Dh2. These could have provided easy conduits for fluid movement and disruption of the Re-Os system. Additionally the Dh5 core is less indurated than its equivalents in Dh2. The chemistry of redox sensitive elements and various proxies are much more scattered in Dh5 indicating post-depositional alteration (Fig. 8, 10).

Cretaceous magmatic intrusions near Dh5 could have expelled or mobilized Re- and Os-bearing fluidsthat disturbed the Re-Os geochronometer. This could account for the Early Cretaceous ages

of the Lardyfjellet Member of Dh5. While no intrusive body was recorded in the Lardyfjellet

Member at Dh5, several dolerite sills were identified from ~849-950 m in the adjacent Dh4

(Senger et al., 2014b). Nevertheless, the dolerite sills have low water contents, and spatially limited thermal areoles, so are not likely as a direct cause of disturbance.

Bioturbation and Re-Os ages

Surprisingly, one of the more robust ages comes from a heavily bioturbated sample, Dh5-

658. Traditionally, bioturbation is interpreted as an indication of oxygenation of the sediment column. Churning alters redox conditions releasing sensitive metals such as Re and Os. In this case, the burrows have been mostly to fully pyritized and/or dolomitized and surrounded by siderite cement. Additionally, vertical burrows do not show compaction textures and horizontal burrows retain nearly equant cross-sections (Fig. 4E). This implies that the section was thoroughly cemented by siderite shortly after burial, preventing significant interaction of fluids with the Re-Os system. Therefore, the Dh5-658 age records a depositional age of Middle to Late

Oxfordian despite heavy bioturbation.

Regional comparisons

Ages of the Lardyfjellet Member of the Agardhfjellet Formation at Longyearbyen show expected correspondence with ages of the Alge Member and middle to lower Krill Member of the Hekkingen Formation (Markey et al., 2017; Georgiev et al., 2017). Although relative uncertainties for Re-Os depositional ages for the Upper Jurassic are at least 0.4% and commonly

>1% (including the 187Re decay constant uncertainty), the nominal ages within a stratigraphic sequence are remarkably consistent. This could indicate that reported age uncertainties may be over-estimated. However, there is more uncertainty in Agardhfjellet ages than in many of their counterparts in the Hekkingen Formation (Markey et al, 2017; Georgiev et al., 2017). Several

possibilities exist to explain these results. Samples with high uncertainties (Dh5-489, 542, and

600) were taken near gradations into courser grained material. The covering sediments could have been affected by locally fluctuating oxygen conditions at the sediment-water interface during deposition which in turn affected fluid conditions in sediment pores below. Any oxidation and removal of Re and Os from the shales by related fluids would have to overcome the abundant organic matter in the Dh5 Lardyfjellet Member samples. As long as a reducing environment was maintained, the shales would rapidly sequester the Re and especially Os from the interacting fluids (Mahdaoui et al., 2015). Although this interaction may disturb the Os isotopic ratios, it also impact the Re/Os ratios proportionately (Hurtig et al., 2016). Thusly, the sediments lock in an early diagenetic age which is indistinguishable from the depositional age.

Variation in the Os ratios on a sub-mm scale from this process could induce some scatter and therefor uncertainty in the reported ages. Another factor in the age uncertainties is the lack of spread in the 187Re/188Os ratios relative to data collection uncertainties. While the Agardhfjellet

Formation has a range of ~90-608 in the 187Re/188Os ratio, individual cores have spreads of less than 50 (e.g., Dh5-600; 353-395) (Appendix C). By comparison, the 187Re/188Os ratio in the

Hekkingen Formation on the margin of the Hammerfest Basin ranges from 550 to 2250 (Markey et al., 2017).

The Agardhfjellet Formation at Longyearbyen has more in common with the Hekkingen

Formation at Troms III (Finmark platform) than in Nordkapp or Hammerfest Basins (southern

Barents Sea). Re-Os geochemistry of the Hekkingen Formation at Troms III has similar concentrations of Re and Os, as well as 187Re/188Re ratios (Georgiev et al., 2017). When compared to the Nordkapp and Hammerfest Basins, the Agardhfjellet is relatively depleted in most redox elements including Re and Os (Markey et al,. 2017; Georgiev et al., 2017).

Sedimentation rates for the Agardhfjellet Formation range from 8.7 m/My to 30.8 m/My. These are more similar to calculated depositional rates of the Hekkingen Formation at Troms III (16.8-

13.1 m/My) than to the Hekkingen Formation at Nordkapp (1.3-5 m/My) or Hammerfest Basin

(1.4-4.1 m/My) (Markey et al., 2017; Georgiev et al, 2016). The highest rate (30.8 m/My) is between the upper Lardyfjellet Member and the upper Oppdalssåta Member which includes several of regressive sequences with high clastic input. The paleogeography of the Troms III site was a proximal marine shelf environment, similar to the Agardhfjellet Formation, as opposed to the more distal Nordkapp and Hammerfest Basins.

Implications for the Late Jurassic timescale

Re-Os ages from the Oppdalssåta and Lardyfjellet Members at Longyearbyen are in better agreement with the defined boundaries of the Kimmeridgian from the 2004 Geologic Time

Scale (GTS) than those of the 2012 GTS (Fig. 7). The Agardhfjellet Formation adds to a growing body of Late Jurassic radiometric ages including: (1) lower Kimmeridgian Re-Os results from the Kimmeridge Clay and Hekkingen Formation (154.1 ± 2.2 Ma; Selby, 2007: 154.7 ± 1.1 Ma;

Georgiev et al., 2017), and (2) an upper Oxfordian 40Ar-39Ar age from the Rosso Ammonitico

Veronese Formation of Italy (156.1 ± 0.89 Ma; Pellenard et al., 2013). Combined, these recent radiometric ages suggest revisiting recommended ages for Late Jurassic stage boundaries, especially the Kimmeridgian-Oxfordian, which are currently calibrated by cyclostratigraphy and magnetostratigraphy.

Anoxia and Restriction

Sections of the Agardhfjellet Formation analyzed for this paper represent times of anoxic to dysoxic conditions. Many of the proxies used to indicate sediment and water column anoxia show oxic conditions; however, it is important to remember that these may be affected by

additional influences. Samples from the Oppdalen Members plot in the oxic section for many proxies traditionally used to characterize bottom water oxygenation. However, this core has delivered the Re-Os age with the least uncertainty. Pyritized burrows and siderite cement of the

Oppdalen Member are better indications of anoxic conditions within the sediment column.

Chemical parameters and framboid analyses from the upper Lardyfjellet Member indicate that sediment pore waters were generally anoxic/sulfidic to dysoxic (Fig. 10). A few thin (<1 mm) intervals of both Dh2 674 and Dh5 613 indicate a possible anoxic water column in addition to sediment anoxia, as the disseminated framboids have a diameter of less than 5 µm (Fig. 10E).

Partial to full pyritization of fossils also indicates anoxic sediment Recrystallization of carbonate bioclasts into dolomite and high-Fe dolomite are additional indications of a persistently reducing environment in which methanogensis is a dominant process. Post-depositional influences on the

Lardyfjellet Member in Dh5 could have created the variability in redox sensitive elements and/or proxies.

Mid-Late Jurassic Climate Shift

13 A decrease in δ Corg and a corresponding increase in Osi indicate a shifting climate over

13 the late Jurassic. The decrease in δ Corg from the Agardhfjellet Formation over the Late Jurassic agrees with both organic and inorganic δ13C trends observed by previous workers, not only in the

Boreal realm (Koevoets et al., 2016; Markey et al., 2017), but throughout the globe (Weissert and Mohr, 1996; Weissert and Erba, 2004; Price et al., 2016). The trend has been interpreted by previous workers as a decrease in burial of organic material and increase in rainfall. The TOC of the Agardhfjellet Formation steadily decreases from the Lardyfjellet Member up through the

Slottsmøya Member echoing these findings. Evidence for increased rainfall comes from the Osi

parameter. Increases in Osi from the Agardhfjellet Formation correspond well with regional trends from several correlative formations (Fig. 11). This increase over the Middle to Late

Figure 11-Composite Osi from Middle Jurassic to Early Cretaceous. Osi reported for this study are from calculated from depositional isochrons. Increasing Osi throughout the Late Jurassic indicates increased continentally derived input into the oceans.

Jurassic is interpreted as increased continental weathering through this time. On their own, global events such as the development of the East Pacific Rise and spreading due to the breakup of Pangea cause a decrease in Osi due to the increased mafic input to the oceanic systems.

However, Cordilleran mountain building (e.g. Nevadan orogeny and Wrangelian arc volcanism) together with several collisional events along southern Eurasia, provide not only weathering potential but subduction related volcanic input contributing to the positive shift in Osi. Coupling

13 δ C trends with Osi trends indicate that the combination of changing climate and accelerated continental margin tectonism in the Late Jurassic lead to increased continental weathering.

6. CONCLUSION

Through systematically addressing non-isochroneity in the Re-Os system using detailed petrography, CT scans, and additional chemical data, it is possible to tease out useful information about black shales. Using this approach, we show that: (1) deposition of the Agardhfjellet

Formation occurred throughout the Late Jurassic into the Early Cretaceous (157.9 Ma to 141 Ma with the Amoeboceras subkitchini zone lasting from at least 153.2 Ma to 150.9 Ma. (2)

187 188 13 Throughout this time oceanic Os/ Os ratios increased while δ Corg decreased which is also seen globally. These trends indicate a shift in the Late Jurassic climate represented by an increase in continental weathering due to an increase in continental freeboard and/or an increase in rainfall. (3) Anoxic conditions during deposition of the Agardhfjellet Formation were not as persistent as several regional counterparts to the south: this most likely results from proximal shelf deposition with shifting oxygen minimum zones and intermittent sediment influx.

Regionally, the Agardhfjellet Formation shares the most in common with the Hekkingen

Formation at the Troms III locality which was also deposited on a marine shelf, with proximal sediment sources. Here we have used Re-Os geochronology to date a Late Jurassic formation, record temporal changes in anoxia within a basin, and infer changing climactic conditions and/or increased global tectonism by linking temporal trends in initial 187Os/188Os ratios to continental weathering rates.

REFERENCES

Abbink, O., Targarona, J., Brinkhuis, H., Visscher, H., 2001. Late Jurassic to earliest Cretaceous palaeoclimactic evolution of the southern North Sea. Global Planet. Change. 20, 231-256. PII: S0921-8181(01)00101-1

Algeo, T.J., Rowe, H., 2012. Paleoceanographic applications of trace-metal concentration data. Chem. Geol. 324-325, 6-18. doi:10.1016/j.chemgeo.2011.09.002

Braathen A., Bergh., S.G. Maher Jr., H.D., 1999. Application of a critical edge taper model to the Tertiary transpressional fold-thrust belt on Spitsbergen, Svalbard. Geol. Soc. Am. Bull. 111(10), 1468-1485. doi: 10.1130/0016-7606(1999)111<1468:AOACWT>2.3.CO;2

Braathen, A., Bælum, K., Christiansen, H.H., Dahl, T., Eiken, O., Elvebakk, H., Hansen, F., Hanssen, T.H., Jochmann, M., Johansen, T.A., Johnsen, H., Larsen, L., Lie, T., Mertes, J., Mørk, A., Mørk, M.B., Nemec, W., Olaussen, S., Oye, V., Rød, K., Titlestad, G.O.,

Tveranger, J., Vagle, K., 2012. The Longyearbyen CO2 Lab of Svalbard, Norway – initial assessment of the geological conditions for CO2 sequestration. Norw. J. Geol. 92, 353- 376.

Cohen, A.S., Coe, A.L., Bartlett J.M., Hawkesworth, C.J., 1999. Precise Re-Os ages of organic- rich mudrocks and the Os isotope composition of Jurassic seawater. Earth Planet. Sci. Lett. 167(3-4), 159-173.

Cohen, A.S., 2004. The rhenium-osmium isotope system: applications to geochronological and paleoenvironmental problems. J. Geol. Soc, London. 161, 729-734.

Cope, J.C.W., 2008. Drawing the line: the history of the Jurassic-Cretaceous boundary. Proceedings of the Geologists Association. 119(1), 105-117.

Creaser R.A., Sannigrahi, P., Chacko, T., Selby, D., 2002. Further evaluation of the Re-Os geochronometer in organic-rich sedimentary rocks: A test of hydrocarbon maturation effects in the Exshaw Formation, Western Canada Sedimentary Basin. Geochim. Cosmochim. Acta. 66(19), 3441-3452. PII S0016-7037(02)00939-0

Crucius, J., Calvert, S., Pedersen, T., Sage, D., 1996. Rhenium and molybdenum enrichments in sediments as indicators of oxic, suboxic and sulfidic conditions of deposition. Earth Planet. Sci. Lett. 145, 65-78.

Ditchfield, P.W., 1997. High northern palaeoaltitude Jurassic-Cretaceous palaeotemperature variation: new data from Kong Karls Land, Svalbard. Palaeogeogr. Palaeoclimatol. Palaeoecol. 130, 163-175. PH S0031-0182(96)00054-5

Dypvik, H., 1985. Jurassic and Cretaceous Black Shales of the Janusfjellet Formation, Svalbard, Norway. Sediment. Geol. 41, 235-248.

Dypvik, H., Nagy, J., Eikeland, T.A., Backer-Owe, K., Andresen, A., Haremo, P., Bjærke, T., Johansen, H., Elverhøi, A., 1991. The Janusfjellet subgroup (Bathonian to Hauterivian) on central Spitsbergen—a revised lithostratigraphy. Polar Res. 9, 21–43.

Dypvik, H., Håkansson, E., Heinberg, C., 2002. Jurassic and Cretaceous palaeogeography and stratigraphic comparisons in the North Greenland-Svalbard Region. Polar Res., 21(1), 91- 108.

Finlay, A.J., Selby, D., Gröcke, D.R., 2010. Tracking the Hirnantian glaciation using Os isotopes. Earth Planet. Sci. Lett. 293, 339-348. doi:10.1016/j.epsl.2010.02.049

Georgiev S., Stein, H.J., Hannah, J.L., Bingen, M., Weiss, H.M., Piasecki, S., 2011. Hot acidic Late Permian seas stifle life in record time. Earth Planet. Sci. Lett. 310(3-4), 389-400.

Georgiev S., Stein, H.J., Hannah, J.L., Weiss, H.M., Bingen, B., Xu, G., Rein, E., Hatlø, V., Løseth, H., Nali, M., Piasecki, S., 2012. Chemical signals for oxidative weathering predict Re-Os isochroneity in black shales, East Greenland. Chem. Geol. 324-325, 108- 121. doi:10.1016/j.chemgeo.2012.01.003

Georgiev, S.V., Stein, H.J., Hannah, J.L., Henderson, C.M., Algeo, T.J., 2015. Enhanced recycling of organic matter and Os-Isotopic evidence for multiple magmatic of meteoric inputs to the Late Permian Panthalassic Ocean, Opal Creek, Canada. Geochim. Cosmochim. Acta. 150, 192-210. http://dx.doi.org/10.1016/j.gca.2014.11.019

Georgiev S.V., Stein, H.J., Hannah, J.L., Xu, G., Bingen, B., Weiss, H.M., 2017. Timing, duration, and causes for Late Jurassic-Early Cretaceous anoxia in the Barents Sea. Earth Planet.Sci.Lett. 461(1), 151-162. http://dx.doi.org/10.1029/2009GC002788

Gradstein F.M., Ogg, J.G., Schmitz, M., Ogg, G. (Eds.) 2012. The Geologic Time Scale 2012 two-volume set. Elsevier, Oxford. 731-779.

Gröcke D.R., Price, G.D., Ruffell, A.H., Mutterlose ,J., Baraboshkin, E., 2003. Isotopic evidence for Late Jurassic-Early Triassic climate change. Palaeogeogr. Palaeoclimatol. Palaeoecol. 202, 97-118. doi:10.1016/S0031-0182(03)00631-X

Hannah., J.L., Georgiev, S., Xu, G., Stein, H.J., 2012, A global Os isotope signal in a narrow seaway – the Late Jurassic from the Barents Sea to S. England. Mineralogical Magazine. 76, 1807.

Hammer, Ø., Collignon, M., Nakrem, H.A., 2012. Organic carbon isotope chemostratigraphy and cyclostratigraphy in the Volgian of Svalbard. Norw. J. Geol. 92, 103-112.

Hammer, Ø., 2014. Initial stratigraphic columns and biostratigraphy for DH2 and DH5R, Adventdalen. written communication.

Heumann, K., 1988. Isotope dilution mass spectrometry. In: Adams, F., Gijbels, R., Van Greiken, R. (Eds.), Inorganic Mass Spectrometry. Wiley Interscience, New York. pp. 301–376.

Hurtig, N.C., Stein, H.J., Hannah, J.L., 2016. Re-Os systematics at the water-oil interface from an experimental perspective. Geol. Soc. America Abstracts with Programs 48:7, doi: 10.1130/abs/2016AM-283562

Kendall B., Creaser, R.A., Gordon, G.W., Anbar, A.D., 2009. Re-Os and Mo isotope systematics of black shales from the Middle Proterozoic Velkerri and Wollogorang Formations, McArthur Basin, northern Australia. Geochim. Cosmochim. Acta. 73, 2534-2558. doi:10.1016/j.gca.2009.02.013

Koevoets M.J., Abay, T.B., Hammer, Ø., Olaussen, S., 2016. High-resolution organic carbon- isotope stratigraphy of the Middle Jurassic-Lower Cretaceous Agardhfjellet Formation of central Spitsbergen, Svalbard. Paleogeogr. Palaoeclimatol. Palaeoecol. 449, 266-274. http://dx.doi.org/10.1016/j.palaeo.2016.02.029

Krajewski, K. P., 2004. Carbon and oxygen isotopic survey of diagenetic carbonate deposits in the Agardhfjellet Formation (Upper Jurassic), Spitsbergen: preliminary results. Pol. Polar Res. 25(1), 27-43.

Lazar, O.R., Bohacs, K.M., Schieber, J., Macquaker, J.H.S., and Demko, T.M., 2015. Mudstone Primer: Lithofacies variations, diagnostic criteria, and sedimentologic-stratigraphic implications at lamina to bedset scales. SEPM Concepts in Sedimentology and Paleontology 12, 198

Lipinski, M., Warning, B., Brumsack, H-J., 2003. Trace metal signatures of Jurassic/Cretaceous black shales from the Norwegian Shelf and Barents Sea. Paleogeogr. Palaoeclimatol. Palaeoecol. 190, 459-475. PII:S0031-0182(02)00619–3

Ludwig, K.R., 2012, Isoplot/Ex Version 3.75, A Geochronological Toolkit for Microsoft Excel. Berkeley Geochronol. Cent. Spec. Publ. 5, 75.

Markey R., Stein, H.J., Hannah, J.L., Georgiev, S.V., Pedersen, J.H., Dons, C.E., 2017. Re-Os identification of glide faulting and precise ages for correlation from the Upper Jurassic Hekkingen Formation, southwestern Barents Sea. Paleogeogr. Palaoeclimatol. Palaeoecol. 466, 209-220. doi:10.1016/j.palaeo.2016.11.032

Michelsen, J.K., Khorasani, G.K., 1991. A regional study on coals from Svalbard: organic facies, maturity and thermal history. Bull. Soc. Geol. France. 162(2), 385-397.

Mahdaoui F., Michels, R., Reisberg, L., Puojol, M., Poirier, Y., 2015. Behavior of Re and Os during contact between an aqueous solution and oil: Consequences for the application of the Re-Os geochronometer to petroleum. Geochim. Cosmochim. Acta. 158, 1-21. doi:10.1016/j.gca.2015.02.009

Marshall, C., Uguna, J., Large, D.J., Meredith, W., Jochmann, M., Friis, B., Vane, C., Spiro, B.F., Snape, C.E., Orheim, A., 2015. Geochemistry and petrology of Paleocene coals form Spitzbergen – Part 2: Maturity variations and implications for local and regional burial models. Int. J. Coal. Geol. 143, 1-10. doi:10.1016/j.coal.2015.03.013

Mørk, A., Dallmann, W.K., Dypvik, H., Johannessen, E.P., Larssen, G.B., Nagy, J., Nøttvedt, A., Olaussen, S., Pčhelina, T.M., Worsley, D., 1999 Mesozoic lithostratigraphy. In: Dallmann, W.K., (Ed.), Lithostratigraphic lexicon of Svalbard Review and Reconstructions for Nomenclature Use. Upper Palaeozoic to Quaternary Bedrock. Norsk Polarinstitutt Tromsø, Norway. 127-214.

Nagy J., Løfaldli, M., Bäckström, S.A., 1988. Aspects of foraminiferal distribution and depositional conditions in the middle Jurassic to early cretaceous shales in eastern Spitsbergen. Abh. Geol. Bund. 30, 287-300.

Nagy, J., Basov, V.A., 1989. Revised foraminiferal taxa and biostratigraphy of Bathonian to Rhyazanian deposits in Spitsbergen. Micropaleontology. 44(3), 217-255.

Page, K.N., 2008. The evolution and geography of Jurassic ammonoids. Proceedings of the Geologist’s Association. 119(1), 35-57.

Pellenard, P., Nomade, S., Martire, L., De Oliveira Ramalho, F., Monna, F., Guillou, H., 2013. The first 40Ar-39Ar date from Oxfordian ammonite-calibrated volcanic layers (bentonites) as a tie-point for the Late Jurassic. Geol. Mag. 150(06), 1136-1142.

Price, G.D., Fözy, I., Pálfy, J., 2016. Carbon cycle history through the Jurassic-Cretaceous boundary: A new global δ13C stack. Paleogeogr. Palaoeclimatol. Palaeoecol. 451, 46-61. doi:10.1016/j.palaeo.2016.03.016

Ravizza, G., Norris, R.N., Blusztajn, J., 2001. An osmium isotope excursion associated with the late thermal maximum: Evidence of intensified chemical weathering. Paleoceanography. 16(2), 155-163.

Ravizza, G., Turekian, K.K., 1989. Application of the 187Re-187Os system to black shale geochemistry. Geochim. Cosmochim. Acta. 53, 3257-3262.

Rooney, A.D., Selby, D., Houzay, J-P., Renne, P.R., 2010. Re-Os geochronology of a Mesoproterozoic sedimentary succession, Taoudeni basin, Mauritania: Implications for

basin-side correlations and Re-Os organic rich sediments systematics. Earth Planet. Sc. Lett. 289, 486-496. doi:10.1016/j.epsl.2009.11.039

Selby, D., 2007. Direct Rhenium-Osmium age of the Oxfordian Kimmeridgian boundary, Staffin Bay, Isle of Skye, UK., and the Late Jurassic time scale. Norw. J. Geol. 87(3), 291-299.

Selby, D., Creaser, R.A., 2003a. Re-Os geochronology of organic rich sediments: an evaluation of organic matter analysis methods. Chem. Geol. 200, 225-240. doi:10.1016/S0009- 2541(03)00199-2

Selby, D., Creaser, R.A., 2003b. Direct Radiometric dating of the Devonian-Mississippian timescale boundary using the Re-Os black shale geochronometer. Geology. 33(7), 545-548. doi: 10.1130/G21324.1

Senger, K., Tveranger, J., Ogata, K., Braathen, A., Planke, S., 2014a. Late Mesozoic magmatism in Svalbard: A Review. Earth-Sci. Rev. 130, 121-144. doi:10.1016/j.earscirev.2014.09.002

Senger K., Planke, S., Polteau, S. Ogata, K., Svensen, H., 2014b. Sill emplacement and contact metamorphism in a siliciclastic reservoir on Svalbard, Arctic Norway. Norw. J. Geol. 94, 155-169.

Smelror M., Mørk, A., Mørk, M.B.E., Weiss, H.M., Løseth, H., 2001. Middle Jurassic-Lower Cretaceous transgressive-regressive sequences and facies distribution off northern Nordland and Troms, Norway. Norwegian Petroleum Society Special Publications 10, 211-232.

Torsvik, T.H., Carlos, D., Mosar, J., Cocks, L.R.M., Maime, T. 2002. Global reconstructions and North Atlantic paleogeography 440 Ma to recent. In: Eide, E.A. (Ed.) BATLAS – Mid Norway Plate Reconstruction Atlas with Global and Atlantic Perspectives. Geological Survey of Norway, Trondheim, pp. 18-39

Tribovillard, N., Algeo, T.J., Lyons, T., Riboulleau, A., 2006. Trace metals as paleoredox and paleoproductivity proxies: An update. Chem. Geol. 232(1). 12-32. doi:10.1016/j.chemgeo.2006.02.012

Turgeon, S.C., Creaser, R.A., 2008. Cretaceous oceanic anoxic event 2 triggered by a massive magmatic episode. Nature. 454, 323-326. doi:10.1038/nature07076

Wedepohl, K.H., 1971. Environmental influences on the chemical composition of shales and clays. In: Ahrens, L.H., Press, F., Runcorn, S.K., Urey, H.C., (Eds.) Physics and Chemistry of the Earth. Pergamon. Oxford. 305-333.

Weissert, H., Mohr, H., 1996. Late Jurassic climate and its impact on carbon cycling. Paleogeogr. Palaoeclimatol. Palaeoecol. 122, 27-43.

Weissert, H., Erba, E.B, 2004. Volcanism, CO2 and palaeoclimate: a Late Jurassic-Early Cretaceous carbon and oxygen isotope record. J. Geol. Soc. London. 161, 695-702.

Wierzbowski, A., Hryniewicz, K., Hammer, Ø., Nakrem, H.A., Little, C.T.S., 2011. Ammonites from hydrocarbon seep carbonate bodies from the uppermost Jurassic – lowermost Cretaceous of Spitsbergen and their biostratigraphical importance. N. Jb. Geol. Paläont. Abh. 262(3), 267-288.

Xu, G., Hannah., J.L., Stein, H.J., Bingen, B., Yang, G., Zimmerman, A., Weitschat, W., Mørk, A., Weiss, H.M., 2009. Re-Os geochronology of Arctic black shales to evaluate the Anisian-Ladinian boundary and global faunal correlations. Earth Planet. Sc. Lett. 288, 581-587. doi:10.1016/j.epsl.2009.10.022

Xu, G., Hannah, J.L., Stein, H.J., Mørk, A., Vigran, J.O., Bingen, B., Schutt, D.L., Lundschien, B.A., 2014. Cause of Upper Triassic climate crisis revealed by Re-Os geochemistry of Boreal black shales. Paleogeogr. Palaoeclimatol. Palaeoecol. 395, 222-232. doi:10.1016/j.palaeo.2013.12.02

Yang, G., Hannah, J.L., Zimmerman, A., Stein, H.J., Bekker, A., 2009. Re-Os depositional age for Archean carbonaceous slates from the southwestern Superior Province: Challenges and insights. Earth Planet. Sci. Lett. 280, 83-92.

APPENDIX A

Table 3-Geochemical Data

Re-Os Geochemistry: AIRIE* Re Blank Os Blank Sample Drill AIRIE 187Os/ Blank Contribution Contribution Depth Hole RUN # Re (ppb) Err (2-s) Re % Error Os (ppb) Os err (2-s) Os % Error 187Re/ 188Os err (2-s) 188Os err (2-s) rho ID % % 489.33 Dh5 ORG-1868 8.5904 0.0832 0.9683 0.3071 0.0002 0.0741 148.3309 1.9784 0.8972 0.0019 0.0744 I 1.5% 0.1% 489.355 Dh5 ORG-1477 10.6884 0.0181 0.1693 0.3170 0.0002 0.0493 181.1404 0.4364 1.0094 0.0014 0.2551 B 0.2% 0.2% 489.4 Dh5 ORG-1429 6.5087 0.1322 2.0318 0.2782 0.0002 0.0542 123.6351 3.4461 0.8681 0.0014 0.0247 A 0.3% 0.3% ORG-1476 6.3560 0.0103 0.1621 0.2808 0.0001 0.0534 119.5181 0.2810 0.8625 0.0013 0.2908 B 0.3% 0.2% 489.44 Dh5 ORG-1478 11.1321 0.0199 0.1787 0.3057 0.0002 0.0808 196.4010 0.5533 1.0403 0.0023 0.3772 B 0.2% 0.2% 489.48 Dh5 ORG-1548 9.7970 0.0944 0.9639 0.3177 0.0005 0.1419 164.8318 2.2209 0.9624 0.0040 0.1306 D 1.2% 0.2% ORG-1479 9.8058 0.0192 0.1961 0.3268 0.0002 0.0653 159.8886 0.4617 0.9390 0.0017 0.2928 B 0.2% 0.2% 542.21 Dh5 ORG-1531 14.3716 0.1357 0.9445 0.2664 0.0003 0.1154 303.2129 3.9750 1.4136 0.0045 0.1099 C 0.8% 0.1% 542.265 Dh5 ORG-1532 22.6133 0.2123 0.9389 0.3438 0.0003 0.0823 379.0687 4.9069 1.6297 0.0036 0.0790 C 0.5% 0.1% 542.305 Dh5 ORG-1430 16.7229 0.0582 0.3482 0.2594 0.0002 0.0852 369.8322 1.8352 1.5894 0.0037 0.1950 A 0.1% 0.3% ORG-1533 16.5213 0.1555 0.9414 0.2570 0.0002 0.0813 369.0497 4.7895 1.5963 0.0035 0.0791 C 0.7% 0.1% 542.38 Dh5 ORG-1534 32.6589 0.3099 0.9488 0.3282 0.0004 0.1143 607.6832 7.9837 2.1771 0.0062 0.1008 C 0.4% 0.1% 542.44 Dh5 ORG-1535 25.5300 0.2377 0.9310 0.2855 0.0002 0.0810 536.9123 6.8867 2.0128 0.0042 0.0742 C 0.5% 0.1% 600.32 Dh5 ORG-1431 26.8950 0.0868 0.3227 0.3890 0.0002 0.0538 393.3956 1.7621 1.5140 0.0022 0.1420 A 0.0% 0.1% ORG-1672 26.9579 0.0605 0.2246 0.3882 0.0005 0.1271 394.7015 1.5390 1.5064 0.0047 0.5095 F 0.5% 0.1% 600.35 Dh5 ORG-1673 24.1325 0.0622 0.2576 0.3846 0.0005 0.1231 353.1076 1.5003 1.4132 0.0041 0.4891 F 0.7% 0.2% 600.355 Dh5 ORG-1869 28.7533 0.1698 0.5906 0.4183 0.0004 0.0940 390.2427 3.2208 1.4924 0.0038 0.1420 I 0.5% 0.1% 600.37 Dh5 ORG-1674 25.6274 0.0682 0.2663 0.3908 0.0004 0.1135 370.8103 1.5771 1.4576 0.0038 0.4689 F 0.6% 0.2% 600.4 Dh5 ORG-1675 30.6349 0.0680 0.2219 0.4519 0.0006 0.1275 384.2806 1.4876 1.4823 0.0047 0.5096 F 0.5% 0.1% 613.53 Dh5 ORG-1571 23.5202 0.0609 0.2588 0.4274 0.0003 0.0675 304.4095 1.1260 1.2613 0.0025 0.2144 E 0.8% 0.2% 613.57 Dh5 ORG-1570 21.5638 0.0506 0.2344 0.3983 0.0002 0.0535 299.0338 0.9855 1.2491 0.0019 0.1971 E 0.9% 0.2% 613.6 Dh5 ORG-1870 23.3720 0.1541 0.6595 0.4503 0.0003 0.0697 285.3726 2.6007 1.2080 0.0024 0.0972 I 0.7% 0.1% 613.64 Dh5 ORG-1569 39.9857 0.0915 0.2288 0.5361 0.0004 0.0688 425.8954 1.4048 1.5543 0.0030 0.2377 E 0.5% 0.1% 613.7 Dh5 ORG-1432 47.1492 0.1117 0.2369 0.6973 0.0005 0.0665 380.7747 1.2983 1.4202 0.0026 0.2506 A 0.0% 0.1% ORG-1568 47.1507 0.1030 0.2184 0.7257 0.0007 0.0899 363.3837 1.2184 1.3620 0.0034 0.3232 E 0.4% 0.1% 613.725 Dh5 ORG-1871 27.5545 0.1734 0.6292 0.4596 0.0003 0.0634 334.2852 2.9026 1.3323 0.0023 0.0935 I 0.6% 0.1% 613.75 Dh5 ORG-1567 28.6529 0.2625 0.9163 0.5002 0.0003 0.0681 317.8705 4.0080 1.2866 0.0025 0.0635 E 0.7% 0.1% 613.78 Dh5 ORG-1566 23.4449 0.0679 0.2895 0.4936 0.0002 0.0402 258.8822 1.0310 1.1353 0.0013 0.1190 E 0.8% 0.1% 658.01 Dh5 ORG-1537 3.8219 0.0251 0.6555 0.2060 0.0001 0.0462 95.2574 0.8580 0.6386 0.0009 0.0625 C 4.9% 0.2% ORG-1549 3.6230 0.0367 1.0129 0.2070 0.0001 0.0486 89.9604 1.2509 0.6370 0.0009 0.0446 D 3.3% 0.3% 658.06 Dh5 ORG-1550 5.1853 0.0540 1.0420 0.2192 0.0002 0.0730 122.9708 1.7636 0.7301 0.0016 0.0626 D 2.3% 0.3% 658.105 Dh5 ORG-1551 8.9197 0.0859 0.9630 0.2273 0.0002 0.1094 209.3330 2.7948 0.9470 0.0031 0.0997 D 1.4% 0.3% 658.14 Dh5 ORG-1552 7.3772 0.0723 0.9800 0.2076 0.0003 0.1518 188.1462 2.5826 0.8977 0.0041 0.1324 D 1.6% 0.3% 658.16 Dh5 ORG-1536 11.7667 0.3027 2.5728 0.2438 0.0015 0.6227 262.2748 9.7696 1.1062 0.0188 0.2268 C 1.6% 0.1% ORG-1553 11.6593 0.1097 0.9412 0.2520 0.0008 0.3243 250.0218 3.5795 1.0636 0.0095 0.3047 D 1.0% 0.3%

660.82 Dh2 ORG-1762 22.6044 0.0489 0.2161 0.2911 0.0002 0.0635 448.6483 1.3926 1.6582 0.0028 0.2501 H 0.6% 0.2% 660.85 Dh2 ORG-1676 30.3977 0.0706 0.2324 0.4001 0.0007 0.1830 437.8051 2.0408 1.6272 0.0075 0.5583 F 0.5% 0.1% ORG-1763 30.1960 0.0693 0.2295 0.4010 0.0003 0.0868 433.4523 1.4979 1.6199 0.0037 0.3128 H 0.4% 0.1% 660.88 Dh2 ORG-1764 18.1800 0.0412 0.2266 0.3025 0.0002 0.0641 336.7195 1.0980 1.3762 0.0024 0.2546 H 0.7% 0.2% 660.915 Dh2 ORG-1872 33.0557 0.1973 0.5970 0.4159 0.0003 0.0647 460.0972 3.7921 1.6700 0.0029 0.0976 I 0.5% 0.1% 660.93 Dh2 ORG-1765 26.1448 0.0573 0.2191 0.4022 0.0002 0.0607 367.2610 1.1524 1.4488 0.0024 0.2494 H 0.5% 0.1% 660.955 Dh2 ORG-1873 24.7190 0.1541 0.6232 0.3616 0.0003 0.0870 388.1518 3.3646 1.4957 0.0035 0.1251 I 0.7% 0.1% 660.96 Dh2 ORG-1766 39.1507 0.0946 0.2416 0.5511 0.0003 0.0635 407.3662 1.4043 1.5823 0.0027 0.2372 H 0.3% 0.1% 660.99 Dh2 ORG-1767 30.8128 0.0661 0.2145 0.4198 0.0003 0.0631 420.8036 1.2999 1.5824 0.0026 0.2615 H 0.4% 0.1% 674.08 Dh2 ORG-1707 42.9179 0.0929 0.2164 0.4908 0.0007 0.1425 512.5796 1.9655 1.7843 0.0067 0.4399 G 0.5% 0.1% 674.1 Dh2 ORG-1708 46.5710 0.0978 0.2100 0.6003 0.0006 0.1052 445.9186 1.5103 1.6082 0.0045 0.3802 G 0.4% 0.1% 674.14 Dh2 ORG-1677 55.7373 0.1295 0.2324 0.6972 0.0008 0.1081 461.5587 1.7269 1.6457 0.0044 0.4299 F 0.3% 0.1% ORG-1709 55.5263 0.1185 0.2134 0.6975 0.0007 0.1000 459.6283 1.5543 1.6477 0.0044 0.3726 G 0.4% 0.1% 674.15 Dh2 ORG-1710 48.9825 0.1084 0.2212 0.5896 0.0005 0.0778 482.6734 1.5773 1.7056 0.0035 0.2864 G 0.4% 0.1% 674.18 Dh2 ORG-1711 55.5162 0.1158 0.2087 0.7320 0.0006 0.0777 435.0198 1.3557 1.5872 0.0033 0.3043 G 0.4% 0.1% Errors for Re and Os data are 2-sigma. Rho is the error correlation between 187Re/188Os and 187Os/188Os. All data are blank corrected using total analyitical blanks (TAB's). * Italics indicate a sample used to determine the proper amount of spiking solution to add in accordance with ideal ratios for isotope dilution spectrometry (See Heumann,

Rock-Eval: Geomark Table 3 cont. Percent Leco Rock-Eval-2 Rock-Eval-2 Rock-Eval-2 Rock-Eval-2 Calculated Hydrogen Oxygen S2/S3 S1/TOC Production Experimental Drill Carbonate TOC S1 S2 S3 Tmax %Ro Index Index Conc. Norm. Oil Index Notations Sample Depth Hole (wt%) (wt%) (mg HC/g) (mg HC/g) (mg CO2/g) (°C) (RE TMAX) (S2x100/TOC) (S3x100/TOC) (mg HC/mg CO2) Content (S1/(S1+S2) 489.33 Dh5 7.518796992 1.69 1.187 1.77 0.39 457 1.066 104.7337278 23.07692308 4.538461538 70.23668639 0.4014204 Low Temp S2 Shoulder 489.355 Dh5 4.007820137 1.98 0.99 2.2 0.23 457 1.066 111.1111111 11.61616162 9.565217391 50 0.3103448 Low Temp S2 Shoulder 489.4 Dh5 1.178781925 2 1.04 2.53 0.22 458 1.084 126.5 11 11.5 52 0.2913165 Low Temp S2 Shoulder

489.44 Dh5 3.742802303 1.83 1.13 1.92 0.24 458 1.084 104.9180328 13.1147541 8 61.74863388 0.3704918 Low Temp S2 Shoulder 489.48 Dh5 1.57116451 2.13 1.08 2.22 0.2 459 1.102 104.2253521 9.389671362 11.1 50.70422535 0.3272727 Low Temp S2 Shoulder

542.21 Dh5 0.472589792 4.71 1.56 4.16 0.18 461 1.138 88.32271762 3.821656051 23.11111111 33.12101911 0.2727273 Low Temp S2 Shoulder 542.265 Dh5 0.280373832 7.59 3.13 7.62 0.2 464 1.192 100.3952569 2.635046113 38.1 41.23847167 0.2911628 Low Temp S2 Shoulder 542.305 Dh5 1.227573182 5.43 1.97 5.93 0.19 461 1.138 109.2081031 3.49907919 31.21052632 36.27992634 0.2493671 Low Temp S2 Shoulder

542.38 Dh5 3.277060576 5.76 2.05 5.97 0.29 461 1.138 103.6458333 5.034722222 20.5862069 35.59027778 0.255611 Low Temp S2 Shoulder 542.44 Dh5 0.294117647 5.67 2.01 5.41 0.27 458 1.084 95.41446208 4.761904762 20.03703704 35.44973545 0.2708895 Low Temp S2 Shoulder 600.32 Dh5 3.297769156 6.36 2.31 5.57 0.21 468 1.264 87.57861635 3.301886792 26.52380952 36.32075472 0.2931472 Low Temp S2 Shoulder

600.35 Dh5 3.62745098 6.39 2.3 5.1 0.27 465 1.21 79.81220657 4.225352113 18.88888889 35.99374022 0.3108108 Low Temp S2 Shoulder 600.355 Dh5 5 6.93 3.14 6.76 0.25 463 1.174 97.54689755 3.607503608 27.04 45.31024531 0.3171717 Low Temp S2 Shoulder 600.37 Dh5 4.147031103 6.65 2.35 5.41 0.32 466 1.228 81.35338346 4.812030075 16.90625 35.33834586 0.3028351 Low Temp S2 Shoulder 600.4 Dh5 3.91221374 7.15 2.57 6.29 0.33 465 1.21 87.97202797 4.615384615 19.06060606 35.94405594 0.2900677 Low Temp S2 Shoulder 613.53 Dh5 1.133144476 8.91 2.66 8.4 0.27 468 1.264 94.27609428 3.03030303 31.11111111 29.85409652 0.2405063 Low Temp S2 Shoulder 613.57 Dh5 1.982160555 8.53 2.47 8.58 0.24 468 1.264 100.5861665 2.813599062 35.75 28.95662368 0.2235294 Low Temp S2 Shoulder 613.6 Dh5 3.80859375 8.88 3.01 7.53 0.38 463 1.174 84.7972973 4.279279279 19.81578947 33.8963964 0.2855787 Low Temp S2 Shoulder 613.64 Dh5 1.744186047 10.3 2.81 9.95 0.39 473 1.354 96.60194175 3.786407767 25.51282051 27.2815534 0.2202194 Low Temp S2 Shoulder 613.7 Dh5 2.032913843 11.7 3.5 10.14 0.35 469 1.282 86.66666667 2.991452991 28.97142857 29.91452991 0.2565982 Low Temp S2 Shoulder

613.725 Dh5 3.677932406 8.86 2.9 7.67 0.42 470 1.3 86.56884876 4.740406321 18.26190476 32.73137698 0.2743614 Low Temp S2 Shoulder 613.75 Dh5 1.857010214 9.05 2.63 8.07 0.25 470 1.3 89.17127072 2.762430939 32.28 29.06077348 0.2457944 Low Temp S2 Shoulder 613.78 Dh5 1.76744186 8.93 2.47 6.94 0.21 468 1.264 77.71556551 2.35162374 33.04761905 27.65957447 0.2624867 Low Temp S2 Shoulder 658.01 Dh5 4.956268222 1.37 0.24 0.49 0.08 466 1.228 35.76642336 5.839416058 6.125 17.51824818 0.3287671

658.06 Dh5 2.367424242 1.42 0.23 0.46 0.1 464 1.192 32.3943662 7.042253521 4.6 16.1971831 0.3333333 658.105 Dh5 2.027027027 1.19 0.21 0.39 0.12 461 1.138 32.77310924 10.08403361 3.25 17.64705882 0.35 658.14 Dh5 3.021442495 1.35 0.24 0.52 0.12 464 1.192 38.51851852 8.888888889 4.333333333 17.77777778 0.3157895 658.16 Dh5 2.799227799 1.34 0.2 0.42 0.1 463 1.174 31.34328358 7.462686567 4.2 14.92537313 0.3225806

660.82 Dh2 6.960784314 6.11 2.3 5.57 0.28 467 1.246 91.16202946 4.582651391 19.89285714 37.64320786 0.292249 Low Temp S2 Shoulder 660.85 Dh2 6.14 8.40 3.13 7.54 0.24 467 1.25 89.76190476 2.857142857 31.41666667 37.26190476 0.2933458 Low Temp S2 Shoulder

660.88 Dh2 5.444126074 6.92 2.5 5.47 0.25 468 1.264 79.04624277 3.612716763 21.88 36.12716763 0.3136763 Low Temp S2 Shoulder 660.915 Dh2 4.875717017 8.19 3.49 7.45 0.39 472 1.336 90.96459096 4.761904762 19.1025641 42.61294261 0.3190128 Low Temp S2 Shoulder 660.93 Dh2 4.592314902 8.17 3.26 7.31 0.36 466 1.228 89.47368421 4.406364749 20.30555556 39.90208078 0.3084201 Low Temp S2 Shoulder 660.955 Dh2 5.044510386 7.73 3.3 6.79 0.35 471 1.318 87.83958603 4.527813713 19.4 42.69081501 0.3270565 660.96 Dh2 3.773584906 10.7 4.3 10.84 0.37 465 1.21 101.3084112 3.457943925 29.2972973 40.18691589 0.2840159 Low Temp S2 Shoulder 660.99 Dh2 3.498542274 8.26 3.19 8.54 0.32 467 1.246 103.3898305 3.87409201 26.6875 38.61985472 0.2719523 Low Temp S2 Shoulder 674.08 Dh2 10.49562682 8.37 2.18 7.49 0.34 466 1.228 89.48626045 4.062126643 22.02941176 26.04540024 0.2254395 Low Temp S2 Shoulder 674.1 Dh2 9.783631232 9.95 2.77 10.02 0.34 466 1.228 100.7035176 3.417085427 29.47058824 27.83919598 0.2165754 Low Temp S2 Shoulder 674.14 Dh2 7.5 11.4 3.09 12.5 0.4 465 1.21 109.6491228 3.50877193 31.25 27.10526316 0.198204 Low Temp S2 Shoulder

674.15 Dh2 3.595080416 9.45 2.55 9.63 0.34 467 1.246 101.9047619 3.597883598 28.32352941 26.98412698 0.2093596 Low Temp S2 Shoulder 674.18 Dh2 6.597549482 11.6 3.02 12.27 0.44 466 1.228 105.7758621 3.793103448 27.88636364 26.03448276 0.1975147 Low Temp S2 Shoulder

Values below detection limits are set at 1/2 the detection limit for plots. % Al in Dh5-658 plots are set at 12% where over the upper detection limit. Table 3 cont. Se Zn Ga As Rb Y Sr Zr Nb Mo In Sn Sb Te Ba La Ce Pr Nd Sm Sample ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm Depth Drill Hole 0.1 0.2 0.1 0.1 0.2 0.1 0.2 1 0.1 0.05 0.1 1 0.1 0.1 1 0.1 0.1 0.1 0.1 0.1 489.33 Dh5 2.4 142 15 22.1 129 20.5 146 141 20.6 2.3 0.1 3 0.5 < 0.1 247 42.1 78.7 7.6 36.1 4.4 489.355 Dh5 2.9 132 24.6 16.1 165 25.4 150 161 37.4 2.26 < 0.1 3 0.6 < 0.1 62 39 76.6 9.8 38.4 6.6 489.4 Dh5 1.8 120 17.2 10.5 170 26.2 154 167 40.6 1.53 < 0.1 3 0.5 < 0.1 259 41.2 78.2 10 39.3 6.9

489.44 Dh5 2.4 159 24.8 23.1 163 26.6 160 164 38.4 2.91 < 0.1 3 0.6 < 0.1 55 39.2 77.5 10.1 39.6 7.2 489.48 Dh5 2.7 144 20 10.8 164 25.2 156 164 37.8 3.62 < 0.1 3 0.6 < 0.1 172 39.8 76.2 9.8 38.2 6.8

542.21 Dh5 4.8 87.6 25 35.1 158 33.5 145 161 26.7 5.85 < 0.1 3 0.9 < 0.1 47 36.8 69.4 9.6 38.1 7.1 542.265 Dh5 7.1 196 24 26.4 152 30.3 147 203 25.3 9.16 < 0.1 3 1 < 0.1 26 36.5 71.3 9.8 38.6 6.8 542.305 Dh5 4.6 137 23 25 131 26.4 141 178 26 4.88 < 0.1 3 0.8 < 0.1 74 33 58.6 8.4 33 5.9

542.38 Dh5 7.6 313 21.6 20.6 132 33.7 164 166 23.6 8.38 < 0.1 3 0.9 < 0.1 63 34.5 65.7 9.2 37.7 7.3 542.44 Dh5 4.6 273 22.1 38.1 123 34.1 158 179 24.7 5.74 < 0.1 3 0.8 < 0.1 68 36.2 66.7 9.6 38.8 7.4 600.32 Dh5 5.3 101 22.6 18.2 137 34.5 200 168 25.2 5.97 < 0.1 3 1.3 < 0.1 83 37.7 68.7 9.7 39 7.2

600.35 Dh5 6.2 99 17.4 18.4 79.6 26.7 153 82 11.6 5.98 < 0.1 3 1.2 < 0.1 63 35.9 63.6 8.9 34.7 6.4 600.355 Dh5 5.9 146 14.4 15.5 109 22.1 152 133 12.4 5.6 0.1 3 1.1 0.1 113 35.9 63.4 6.5 31.7 3.9 600.37 Dh5 5.7 98.7 17 16.1 80.4 26.9 162 77 11.4 5.13 < 0.1 3 1 < 0.1 66 35.7 63.8 9.2 35.4 6.7 600.4 Dh5 6.5 124 18.5 16.7 83.3 30.5 185 86 12 4.66 < 0.1 3 1 < 0.1 74 41.4 75.6 10.8 41.8 8 613.53 Dh5 11 171 22.2 20 123 37.3 241 161 23.3 4.24 < 0.1 3 2 < 0.1 38 35.2 61.4 9.4 37.4 7.1 613.57 Dh5 10 112 22.8 18.3 133 40.2 257 154 24.3 4.05 < 0.1 3 1.8 0.2 53 38 66.4 10 40.3 7.5 613.6 Dh5 10.6 98 14.2 23.7 95.5 29 201 132 12.3 4.8 0.1 3 2 0.1 62 33.9 57.4 7 35.3 4.7 613.64 Dh5 11 349 24.2 21.1 137 36 273 169 25 5.49 < 0.1 3 2.2 < 0.1 42 38.7 68.3 10.1 40.1 7.4 613.7 Dh5 15 733 23.3 28.3 125 40.3 257 160 22.7 17.2 < 0.1 3 2.6 < 0.1 27 36.2 66.4 10.7 44 8.6

613.725 Dh5 9.2 173 14.7 14.3 100 20.7 183 128 12.5 4.4 0.1 3 1.7 0.1 139 34.1 52.6 6 28.5 3.3 613.75 Dh5 11.7 202 24.1 21.3 138 34.4 237 157 24.1 5.41 < 0.1 3 2.2 < 0.1 36 36.7 65.4 9.5 37.7 6.4 613.78 Dh5 12.8 224 23 24.8 122 40.2 227 151 22.8 4.96 < 0.1 3 2.3 < 0.1 33 33.6 61.6 9.5 39.5 7.6 658.01 Dh5 < 0.1 130 21.7 22.6 153 25.3 166 183 30.7 1.34 < 0.1 3 0.6 < 0.1 147 34 74.8 8.8 34.6 6.6

658.06 Dh5 0.1 123 24.9 28.1 154 24.5 145 179 29.9 1.61 < 0.1 3 0.7 < 0.1 53 30.4 70.7 8.3 32.9 6.1 658.105 Dh5 0.8 130 25.5 21.9 144 24.9 163 174 30.2 1.47 < 0.1 3 0.6 0.2 40 30.5 71.1 8.5 33.4 6.3 658.14 Dh5 < 0.1 145 20.4 20.3 153 24.9 161 180 30 1.01 < 0.1 3 0.6 < 0.1 148 32.2 71.2 8.4 33.3 6.2 658.16 Dh5 < 0.1 150 24.3 29.4 156 25.1 166 179 29.2 1.5 < 0.1 3 0.6 0.1 46 30.4 69.6 8.3 33.4 6.3

660.82 Dh2 6.5 243 14.3 13.4 66 26.2 132 75 9.8 4.65 < 0.1 3 1 < 0.1 135 31.3 53.6 7.9 31.3 5.6 660.85 Dh2 8.3 166 16.8 19.3 63 25.9 129 91 11.2 5.6 < 0.1 3 1.2 < 0.1 61 31.5 53.7 7.7 30 5.7

660.88 Dh2 7.1 122 17.2 16.3 86.2 26.3 123 81 11.3 3.77 < 0.1 3 1.2 < 0.1 68 32.3 53.2 7.6 29.2 5.5 660.915 Dh2 7.7 227 13.3 15.1 96.3 24.6 135 136 11.6 4.9 < 0.1 3 1.3 0.1 137 34.8 57.7 6.6 31.6 4 660.93 Dh2 8.9 122 16.6 46.8 75.3 27.6 128 81 11.3 5.6 < 0.1 3 1.4 < 0.1 57 33.3 55.5 8.2 31.3 5.9 660.955 Dh2 7.3 139 14.1 16.7 85.3 24.7 134 142 12.2 4.6 0.1 3 1.3 0.1 93 36.7 59.6 6.5 31.5 4 660.96 Dh2 11.8 523 17.1 29.2 84 26.4 132 87 10.6 6.45 < 0.1 3 1.6 0.1 68 31 51.3 8.1 32.2 6 660.99 Dh2 8.2 151 18.2 18.3 87.2 27.8 126 79 11.3 5.27 < 0.1 3 1.3 < 0.1 85 32.9 51.7 8 31.4 5.8 674.08 Dh2 10.6 482 13.9 20.2 77 49.8 197 70 9 11.2 < 0.1 3 2 < 0.1 99 44.9 67.9 11.2 45 8.8 674.1 Dh2 11.3 363 13.7 18.5 64.2 42.6 167 66 8.9 11.6 < 0.1 3 2.1 < 0.1 83 38.7 58.1 9.7 38.5 7.7 674.14 Dh2 12.8 561 16.9 17.2 80.5 45.8 169 45 9.4 10.9 < 0.1 3 2.1 < 0.1 98 42.2 63 10.6 42.9 8.4

674.15 Dh2 12.6 246 15.4 19.6 84.8 37.9 147 74 10.3 9.08 < 0.1 3 1.9 < 0.1 66 39.4 62.6 10 40.1 8.2 674.18 Dh2 13.7 457 15.8 29.6 57.2 42.6 179 74 10.2 9.46 < 0.1 3 2.1 < 0.1 89 40.8 68.4 11.8 49.3 9.4

Trace and Major Elements: ACT Labs. Lower detection limits listed below elements. Readings above and below detection limits are desiganted by > or < respectively. Table 3 cont. Li Na Mg Al K Ca Cd V Cr Mn Fe Hf Hg Ni Er Be Ho Ag Cs Co Eu Bi Sample ppm % % % % % ppm ppm ppm ppm % ppm ppb ppm ppm ppm ppm ppm ppm ppm ppm ppm Depth Drill Hole 0.5 0.01 0.01 0.01 0.01 0.01 0.1 1 0.5 1 0.01 0.1 10 0.5 0.1 0.1 0.1 0.05 0.05 0.1 0.05 0.02 489.33 Dh5 67.9 0.4 1.3 7.7 2.7 0.7 0.2 130 120 136 3.5 3.3 40 54.5 2.3 2.2 0.9 0.7 9.8 11.4 1.3 0.3 489.355 Dh5 101 0.57 1.47 8.91 3.27 0.64 0.3 138 137 142 3.66 6.9 < 10 59.8 2.9 3.2 1 0.74 9.94 10.8 1.27 0.3 489.4 Dh5 105 0.6 1.53 9.38 3.38 0.63 0.3 144 159 152 3.24 7.2 < 10 48.9 2.9 3.2 1 0.64 10.4 9.7 1.29 0.3

489.44 Dh5 96.1 0.6 1.47 9.06 3.23 0.67 0.4 137 116 123 4 6.9 30 60.7 2.9 3.1 1 0.68 9.79 11.4 1.35 0.28 489.48 Dh5 96.9 0.64 1.35 8.99 3.23 0.45 0.4 136 132 125 3.09 7 70 58.6 2.8 2.9 0.9 0.75 9.87 10.5 1.24 0.29

542.21 Dh5 63.4 0.53 1.06 9.09 3.67 0.39 0.7 159 132 93 3.41 6.7 10 70.6 3.4 3.2 1.2 0.75 9.22 10.2 1.44 0.28 542.265 Dh5 67.6 0.52 0.95 8.68 3.44 0.22 2.5 170 198 104 3.94 7.6 70 91.6 3.3 2.9 1.1 1.72 8.76 10.2 1.3 0.32 542.305 Dh5 64.4 0.51 0.97 9.22 3.04 0.3 1.2 162 185 96 2.91 6.9 60 62.5 2.8 3.2 0.9 1.22 8.41 9 1.17 0.3

542.38 Dh5 63.3 0.5 1.04 7.91 3.11 0.43 5.2 139 166 146 3.48 6.6 80 77.2 3.4 2.5 1.2 1.83 7.97 8.8 1.43 0.29 542.44 Dh5 61.6 0.52 0.94 8.73 2.72 0.29 4.1 146 181 89 3.09 6.9 50 66.9 3.5 2.8 1.2 1.27 7.96 9.5 1.39 0.28 600.32 Dh5 70 0.51 1.03 9.31 3.1 0.5 0.4 167 166 107 2.46 6.9 50 63.8 3.5 3.2 1.2 1.22 8.81 8.4 1.34 0.27

600.35 Dh5 74 0.39 0.93 8.12 2.09 0.39 0.5 161 111 102 2.67 3.6 50 71.1 3.2 2.9 1 2 8.82 7.5 1.27 0.28 600.355 Dh5 41.3 0.3 0.8 7.2 2.9 0.4 0.6 143 118 157 2.6 2.9 100 70.3 2.4 1.9 0.9 1.1 8.3 9.1 1.2 0.3 600.37 Dh5 73.9 0.38 0.88 7.57 2.04 0.38 0.5 160 105 91 2.59 3.5 60 66.2 3.1 2.8 1 1.5 8.8 7 1.3 0.27 600.4 Dh5 80.5 0.4 0.91 7.9 2.24 0.37 0.7 170 116 97 2.49 3.6 50 71.5 3.4 2.9 1.1 1.53 9.58 7.5 1.54 0.28 613.53 Dh5 70.4 0.47 0.94 8.44 2.8 0.42 1.4 268 178 103 2.88 6.4 70 71 3.7 3.1 1.2 1.8 8.34 8.1 1.35 0.27 613.57 Dh5 73.7 0.48 1.03 9.02 2.89 0.47 0.7 275 129 108 2.44 6.2 50 65.4 3.9 3.2 1.4 1.61 8.77 7.8 1.48 0.27 613.6 Dh5 45.1 0.3 0.8 6.7 2.6 0.4 0.6 228 136 94 2.9 2.9 150 77.5 2.9 2.1 1.1 2 7.6 8.4 1.5 0.3 613.64 Dh5 77.5 0.48 1.04 9.26 2.95 0.36 3.8 305 159 118 2.49 6.6 < 10 86.5 3.7 3.3 1.2 2.6 9.13 9 1.36 0.29 613.7 Dh5 71.7 0.45 0.93 8.2 2.69 0.39 9.6 278 189 111 3.11 6.1 20 152 3.9 3.2 1.4 3.13 8.06 10.1 1.63 0.28

613.725 Dh5 46.1 0.3 0.7 7.2 2.8 0.3 1.4 237 135 91 2 2.9 110 70.2 2.2 2.1 0.8 1.8 8.4 8.6 1 0.3 613.75 Dh5 75 0.46 0.97 8.95 2.95 0.34 1.8 266 144 72 2.7 6.2 100 81.4 3.5 3.3 1.2 2.05 9.11 9.1 1.22 0.29 613.78 Dh5 71 0.44 0.92 8.7 2.73 0.37 2.7 258 173 73 3.14 6.1 130 82 3.9 3.2 1.3 2.11 8.2 8.4 1.51 0.28 658.01 Dh5 128 0.57 1.18 > 10.0 2.96 0.33 0.1 173 71.1 169 3.6 7.7 120 47.1 2.9 3.2 1 0.86 10.6 11 1.19 0.45

658.06 Dh5 126 0.57 1.17 > 10.0 3.16 0.33 < 0.1 168 79.8 208 4.48 7.7 130 53.9 2.8 3 0.9 0.69 10.1 11.3 1.15 0.44 658.105 Dh5 123 0.55 1.17 > 10.0 2.79 0.34 0.1 166 74 233 4.43 7.6 180 49.4 2.8 3.3 0.9 0.72 9.86 10.4 1.15 0.44 658.14 Dh5 125 0.55 1.16 9.98 3.06 0.33 0.2 167 89 151 3.27 7.6 60 37.7 2.9 3.2 1 0.55 9.87 10.4 1.17 0.43 658.16 Dh5 126 0.56 1.16 > 10.0 3.14 0.34 0.2 159 85.6 197 4.41 7.5 150 55.2 2.8 3.1 1 0.53 9.68 12.1 1.13 0.41

660.82 Dh2 80.6 0.38 0.92 6.38 1.63 0.76 1.8 163 104 128 2.31 3.2 70 57.2 2.8 2.1 1 1.98 6.2 5.9 1.18 0.2 660.85 Dh2 79.5 0.34 0.87 6.72 1.62 0.59 1.2 187 122 116 2.57 3.5 110 71.7 2.9 2.5 0.9 2.34 7.17 6.9 1.12 0.27

660.88 Dh2 76.7 0.37 0.89 6.96 2.58 0.59 0.7 192 118 106 2.43 3.3 20 55.3 2.8 2.4 0.8 1.27 7.87 6.8 1.09 0.28 660.915 Dh2 48.7 0.3 0.8 6.9 2.6 0.7 1.5 170 135 111 2.35 3 100 67.3 2.5 1.8 1 2.1 6.95 7.8 1.25 0.3 660.93 Dh2 78.7 0.33 0.86 6.89 1.95 0.57 0.8 198 120 118 2.93 3.3 110 71.1 3 2.7 0.9 2.57 7.61 7.5 1.15 0.27 660.955 Dh2 50.9 0.3 0.9 7.2 2.1 0.7 0.8 174 141 118 2.5 3.1 100 65.5 2.7 2 1 1.8 7.2 8.1 1.3 0.3 660.96 Dh2 81.3 0.32 0.82 6.75 2.54 0.54 5.7 207 132 99 2.65 3.4 60 90.7 3 2.5 0.9 3.89 7.14 6.9 1.17 0.27 660.99 Dh2 83.1 0.35 0.81 7.02 2.67 0.53 1 212 132 115 2.35 3.3 80 70.7 3 2.7 1 3.08 8.03 7 1.16 0.29 674.08 Dh2 58.8 0.38 1.3 5.91 2.11 1.94 6.8 271 108 163 2.36 2.9 40 84.5 4.8 2.2 1.5 2.81 6.19 6 1.81 0.21 674.1 Dh2 54 0.34 1.08 5.67 1.84 1.59 5.3 275 113 149 2.06 2.6 50 88 4.2 2.2 1.3 3.87 5.85 5.8 1.55 0.24 674.14 Dh2 61 0.37 1.04 6.99 2.24 1.24 9 336 147 121 2.08 0.9 50 103 4.5 2.6 1.5 4.41 7.44 6.5 1.68 0.27

674.15 Dh2 63.8 0.37 0.78 6.76 2.35 0.74 3 303 124 112 2.24 3.1 40 93.3 4 2.8 1.2 3.28 7.67 6.7 1.52 0.26 674.18 Dh2 63.7 0.36 0.87 6.13 1.54 1 6.6 310 128 128 2.34 3.1 20 99.2 4.3 2.8 1.4 4 7.19 6.3 1.9 0.28

Table 3 cont. Gd Tb Dy Cu Ge Tm Yb Lu Ta W Re Tl Pb Sc Th U Ti P S Sample ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm % % % Depth Drill Hole 0.1 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.001 0.05 0.5 1 0.1 0.1 0.0005 0.001 0.01 489.33 Dh5 5.1 0.7 3.8 53.6 < 0.1 0.3 2.3 0.4 1.1 1.1 < 0.001 0.7 21.7 18 12.5 4.2 0.56 0.058 1.53 489.355 Dh5 4.9 0.7 4.8 49.2 < 0.1 0.4 2.9 0.4 3.4 4.7 0.003 0.84 19.3 19 11.3 3.4 0.551 0.053 1.59 489.4 Dh5 5 0.8 5 45.8 < 0.1 0.4 3 0.4 3.7 2.4 < 0.001 0.81 19.5 20 12.5 3.4 0.599 0.057 0.99

489.44 Dh5 5.3 0.8 5.1 49.2 < 0.1 0.4 2.9 0.4 3.5 2.5 0.006 0.85 19.8 18 10.5 3.5 0.533 0.054 1.98 489.48 Dh5 4.8 0.7 4.7 52.8 < 0.1 0.4 2.9 0.4 3.3 2.2 0.005 0.85 18.4 17 11.8 3.4 0.529 0.049 1.1

542.21 Dh5 5.9 0.9 5.9 55.4 < 0.1 0.5 3.3 0.5 2.7 2.2 0.007 1.06 19.4 17 10.4 5 0.52 0.079 2.57 542.265 Dh5 5.2 0.8 5.4 72 < 0.1 0.5 3.3 0.5 2.6 1.8 0.015 1.43 23.9 17 9.7 5.5 0.499 0.058 3.26 542.305 Dh5 4.6 0.7 4.6 52.4 < 0.1 0.4 2.8 0.4 2.6 2 0.009 0.99 18.6 17 8.3 4.1 0.516 0.061 1.97

542.38 Dh5 5.9 0.9 5.8 62.5 < 0.1 0.5 3.3 0.5 2.4 1.7 0.022 1.36 20.2 15 8.7 4.9 0.498 0.081 2.43 542.44 Dh5 5.8 0.9 5.9 51.7 < 0.1 0.5 3.3 0.5 2.5 2 0.016 1.14 18.7 17 9.1 4.5 0.534 0.079 2.36 600.32 Dh5 5.5 0.9 5.6 42.7 < 0.1 0.5 3.6 0.5 2.5 1.9 0.017 0.79 15.9 17 10.3 5.1 0.566 0.085 1.88

600.35 Dh5 5.5 0.8 5.1 52.9 < 0.1 0.5 3 0.6 0.9 1.4 0.022 0.95 18.2 14 11 5.4 0.524 0.071 2.52 600.355 Dh5 4.9 0.7 3.8 51.1 < 0.1 0.3 2.3 0.4 0.8 0.9 < 0.001 0.7 17.7 15 9.7 3.7 0.527 0.068 2.31 600.37 Dh5 5.7 0.8 5 46.9 < 0.1 0.5 2.9 0.5 0.8 1.2 0.022 0.77 17.7 14 11.1 5.4 0.509 0.067 2.29 600.4 Dh5 6.7 0.9 5.8 52.5 < 0.1 0.5 3.1 0.5 0.8 1.2 0.028 0.83 18.5 14 12.5 6 0.524 0.068 2.08 613.53 Dh5 5.8 0.9 6.1 62.8 < 0.1 0.5 3.5 0.5 2.3 1.9 0.016 0.71 18.5 17 8.9 4.9 0.539 0.091 2.84 613.57 Dh5 6.4 0.9 6.5 53.7 < 0.1 0.6 3.8 0.6 2.4 2 0.013 0.75 19 17 9.9 5.5 0.544 0.098 2.16 613.6 Dh5 6.3 0.9 4.8 60.8 < 0.1 0.3 2.5 0.4 0.7 1 < 0.001 0.6 19.3 14 7.2 4 0.507 0.103 3.07 613.64 Dh5 5.7 0.8 5.8 63.1 < 0.1 0.5 3.7 0.6 2.5 2 0.032 1.02 19 18 10.1 6 0.591 0.068 2.42 613.7 Dh5 6.8 1 6.7 81.4 < 0.1 0.6 3.6 0.5 2.3 1.9 0.038 1.59 19.2 16 9 6.1 0.521 0.078 3.2

613.725 Dh5 4 0.6 3.2 59 < 0.1 0.3 2.2 0.4 0.7 1 < 0.001 0.7 20.7 15 7.9 3.5 0.548 0.053 1.87 613.75 Dh5 5.1 0.8 5.5 57.7 < 0.1 0.5 3.6 0.6 2.4 1.9 0.019 0.81 20.5 17 9.8 5.7 0.531 0.058 2.49 613.78 Dh5 6.4 1 6.5 56.8 < 0.1 0.5 3.6 0.5 2.3 1.9 0.015 0.87 20.1 16 8.1 5 0.524 0.082 3.13 658.01 Dh5 4.6 0.7 4.8 34.7 < 0.1 0.4 3 0.5 2.9 2.5 < 0.001 0.77 24.6 18 11.5 3.2 0.593 0.052 1.35

658.06 Dh5 4.3 0.7 4.6 38.2 < 0.1 0.4 2.9 0.4 2.9 2.3 < 0.001 0.83 25.4 18 8.9 3.2 0.573 0.05 2.3 658.105 Dh5 4.5 0.7 4.7 40.5 < 0.1 0.4 2.9 0.4 2.9 2.3 0.003 0.8 21.6 19 8.5 3.2 0.602 0.053 2.46 658.14 Dh5 4.4 0.7 4.6 36.7 < 0.1 0.4 2.9 0.4 2.9 2.2 0.006 0.8 20.3 19 11.2 3.2 0.64 0.057 1.04 658.16 Dh5 4.6 0.7 4.7 37 < 0.1 0.4 3 0.4 2.8 2 0.004 0.84 22.7 18 8.7 3.1 0.595 0.054 2.32

660.82 Dh2 5.3 0.8 4.6 47.7 < 0.1 0.4 2.6 0.5 0.7 1.1 0.02 0.77 14.4 14 10.4 4.8 0.455 0.073 1.75 660.85 Dh2 5 0.7 4.5 62.7 < 0.1 0.4 2.7 0.5 0.8 1.2 0.027 0.92 18.3 14 9.6 4.8 0.502 0.063 2.18

660.88 Dh2 4.8 0.7 4.4 56.2 < 0.1 0.4 2.7 0.5 0.8 1.3 0.016 0.69 18.4 14 10.5 4.2 0.507 0.068 1.91 660.915 Dh2 5 0.7 4.1 67.3 < 0.1 0.3 2.5 0.4 0.8 0.9 < 0.001 0.8 16.8 14 9.5 3.8 0.492 0.081 1.98 660.93 Dh2 5.2 0.8 4.7 66.8 < 0.1 0.5 2.9 0.5 0.8 1.2 0.022 0.85 18.4 14 9.4 4.9 0.487 0.071 2.58 660.955 Dh2 5.1 0.7 4.2 58.4 < 0.1 0.3 2.5 0.4 0.8 1 < 0.001 0.7 19.1 15 9.5 3.8 0.513 0.079 2.18 660.96 Dh2 5.4 0.7 4.7 81.8 < 0.1 0.4 2.8 0.5 0.7 1.2 0.036 1.54 17.5 13 9.3 4.6 0.469 0.06 2.42 660.99 Dh2 5.5 0.8 4.9 66.3 < 0.1 0.4 2.7 0.5 0.8 1.3 0.028 0.84 18.6 13 8.7 3.7 0.498 0.071 1.88 674.08 Dh2 8.5 1.2 7.6 56.7 < 0.1 0.7 4.1 0.8 0.7 1.2 0.04 1.66 14.8 15 11.1 10.2 0.408 0.203 2.16 674.1 Dh2 7.3 1 6.5 71.1 < 0.1 0.6 3.7 0.7 0.7 1.1 0.042 1.61 15 15 9.3 9.2 0.426 0.188 2.09 674.14 Dh2 8 1.2 7.1 83.3 < 0.1 0.7 4 0.7 0.5 1.3 0.052 1.84 16.8 15 11 9.8 0.455 0.168 1.9

674.15 Dh2 7 1 6.3 69.5 < 0.1 0.6 3.5 0.6 0.7 1.3 0.043 1.2 18.3 14 10.3 7.4 0.479 0.141 2.32 674.18 Dh2 9 1.3 7.5 77.6 < 0.1 0.6 3.5 0.6 0.7 1.2 0.049 1.32 17.1 15 11.4 15 0.473 0.159 2.34

Stable Isotopes: IsoAnalytical Table 3 cont.

Sample d13CV-PDBd18OV-PDBd13CV-PDB-OElemental N d15NAir Elemental d34SV-CDT Depth Drill Hole (‰) (‰) (‰) (%) (‰) Sulphur (%) (‰) 489.33 Dh5 489.355 Dh5 489.4 Dh5 -8.35 -8.92 -29.63 0.18 3.42 0.99 -18.43

489.44 Dh5 -29.71 0.17 3.46 2.10 -28.17 489.48 Dh5

542.21 Dh5 -7.17 -7.99 -26.89 0.22 3.48 2.71 -29.03 542.265 Dh5 542.305 Dh5

542.38 Dh5 -26.95 0.25 3.43 2.55 -26.40 542.44 Dh5 600.32 Dh5

600.35 Dh5 600.355 Dh5 600.37 Dh5 -7.33 -10.06 -26.21 0.25 4.82 2.60 -22.39 600.4 Dh5 -8.08 -9.49 -26.44 0.27 4.56 2.32 -21.79 613.53 Dh5 613.57 Dh5 613.6 Dh5 613.64 Dh5 -8.83 -12.23 -25.81 0.35 3.99 2.29 -15.95 613.7 Dh5

613.725 Dh5 613.75 Dh5 -7.61 -10.45 -25.96 0.31 4.27 2.65 -11.91 613.78 Dh5 -9.20 -12.03 -25.91 0.32 4.28 3.46 -7.37 658.01 Dh5 -25.25 0.16 3.62 1.34 -33.49

658.06 Dh5 658.105 Dh5 -9.26 -9.79 -25.26 0.16 3.26 2.32 -27.76 658.14 Dh5 658.16 Dh5

660.82 Dh2 -9.42 -12.11 -26.01 0.22 4.52 1.84 -13.53 660.85 Dh2

660.88 Dh2 Dh2 660.93 Dh2 660.955 Dh2 660.96 Dh2 -9.56 -12.89 -26.06 2.81 -16.53 660.99 Dh2 674.08 Dh2 -13.58 -14.54 -26.36 0.30 4.92 2.43 -17.03 674.1 Dh2 674.14 Dh2

674.15 Dh2 -11.80 -13.92 -26.24 0.34 4.77 2.56 -16.73 674.18 Dh2

APPENDIX B

Table 4-Re-Os Total Analytical Blank Data Re Os Blank Re Blank % Os Blank % Blank ID Blank err (2-s) Error Blank err (2-s) Error comp err (2-s) A 6.781 0.056351 0.831003 0.277008 0.004368 1.57677 0.784472 0.010588 B 11.208 0.092217 0.822783 0.277008 0.004368 1.57677 0.784472 0.010588 C 58.818 0.308441 0.524402 0.108 0.016 14.81481 0.225 0.102 D 61.532 0.105538 0.171517 0.321305 0.010668 3.320259 1.025162 0.019333 E 59.125 0.459891 0.77783 0.210274 0.006978 3.318619 2.104842 0.051292 F 56.979 22.46991 39.43562 0.209298 0.237773 113.6051 0.212467 0.108018 G 58.756 0.161245 0.27443 0.193091 0.005116 2.649584 0.286787 0.00744 H 53.13 0.269061 0.506419 0.189874 0.002383 1.255033 0.737742 0.007401 I 59.939 0.197055 0.328759 0.167808 0.004576 2.726737 0.287742 0.006441

APPENDIX C: RE-OS ISOCHRONS